JP4860464B2 - Benzochromene derivatives - Google Patents

Description

  The present invention relates to benzochromene derivatives, preferably mesogenic benzochromene derivatives, in particular liquid crystal benzochromene derivatives and liquid crystal media comprising these benzochromene derivatives. The invention further provides liquid crystal displays, in particular liquid crystal displays addressed by active matrix (AMD or AM LCD (“active matrix addressed liquid crystal display”)) and very particularly so-called VAN (“vertically aligned nematic”) liquid crystal displays, ECB (“electrical Controlled birefringence ") With respect to liquid crystal display embodiments, here nematic liquid crystals with negative dielectric anisotropy (Δε) are used.

  In this type of liquid crystal display, the liquid crystal is used as a dielectric whose optical characteristics change reversibly when a voltage is applied. Electro-optical displays using liquid crystals as media are known to those skilled in the art. These liquid crystal displays use various electro-optic effects. The most common of these is a uniform TN (“twisted nematic”) effect with a flat initial orientation and a nematic structure twisted about 90 °, 180 ° or more twisted, of the liquid crystal director STN (“super twisted nematic”) effect and SBE (“super twist birefringent effect”) effect with nematic structure. In these and similar electro-optical effects, liquid crystal media having positive dielectric anisotropy (Δε) are used.

  In addition to the above-mentioned electro-optical effect that requires a liquid crystal medium having a positive dielectric anisotropy, other electro-optical effects using a liquid crystal medium having a negative dielectric anisotropy, such as the ECB effect and its dependent forms There are DAP ("orientation phase deformation"), VAN and CSH ("color hyperhomeotropic").

  An electro-optic effect having a low viewing angle dependence with excellent contrast uses an axisymmetric micropixel (ASM). In this effect, the liquid crystal in each pixel is surrounded by a polymer material in a cylindrical shape. This scheme is particularly suitable for combination with plasma channel addressing. Thus, in particular, a large area PA (“Plasma Address”) LCD having a good viewing angle dependence of contrast can be achieved.

  Increasingly used IPS ("in-plane switching") effects can use dyes in either dielectrically positive or dielectrically negative media, depending on the display mode used. As with the guest / host display, both dielectrically positive and dielectrically negative liquid crystal media can be used.

  Since the operating voltage including in a general liquid crystal display, ie in a display based on these effects, must be as low as possible, a liquid crystal medium having a large absolute value of dielectric anisotropy is used. Consisting mainly of liquid crystal compounds having a dielectric anisotropy with a corresponding sign, i.e. mainly and very substantially, i.e. compounds having a positive dielectric anisotropy in the case of a dielectrically positive medium, and In the case of a dielectrically negative medium, it consists of a compound having negative dielectric anisotropy. In each type of medium (dielectrically positive or dielectrically negative), at most a significant amount of dielectrically neutral liquid crystal compound is typically used. Liquid crystal compounds having a sign of the dielectric anisotropy opposite to the dielectric anisotropy of the medium are generally used in very small amounts or not completely.

The exception here is formed by liquid crystal media for MIM (“metal-insulator-metal”) displays (Simmons, J G., Phys. Rev. 155 No. 3, pages 657-660 and Niwa, JG et al., SID 84 Digest, pages 304-307, June 1984), where the liquid crystal medium is addressed by an active matrix of thin film transistors. In this type of addressing, which uses a non-linear characteristic curve of diode switching, it is not possible to charge the storage capacitor with the electrode of the liquid crystal display element (pixel), in contrast to a TFT display. Therefore, a reduction in the effect of the voltage drop during the addressing cycle requires the highest possible basic value of the dielectric constant. Thus, for example, as used in MIM-TN displays, in dielectrically positive media, the dielectric constant (ε _垂直 ) perpendicular to the molecular axis should be as large as possible. This is because this determines the basic capacitance of the pixel. For this purpose, a compound having a negative dielectric anisotropy is dielectrically applied in a dielectrically positive liquid crystal medium as described, for example, in WO 93/01253, EP 0 663 502 and DE 195 21 483. Used in addition to the positive compound.

Another exception is the STN display, for example in DE 41 00 287, where a dielectric positive liquid crystal medium comprising a dielectric negative liquid crystal compound is used to increase the steepness of the electro-optical characteristic curve. It is formed by.
The pixels of a liquid crystal display can be addressed directly, continuously in time, i.e. in a time multiplex mode, or by a matrix of active elements having a non-linear electrical characteristic curve.

  The most common AMDs to date are separate active electronic switching elements such as tripolar switching elements such as MOS (“metal oxide silicon”) transistors or thin film transistors (TFTs) or varistors or bipolar switching elements such as MIM ( “Metal insulator metal”) diodes, ring diodes or back diodes are used. In the TFT, various semiconductor materials are used, mainly silicon, but also cadmium selenide. In particular, amorphous silicon or polycrystalline silicon is used.

  In the present application, a liquid crystal display having an electric field perpendicular to the liquid crystal layer and a liquid crystal medium having negative dielectric anisotropy (Δε <0) are preferable. In these displays, the edge alignment of the liquid crystal is homeotropic. In the fully connected state, ie when applying a correspondingly high voltage, the liquid crystal director is aligned parallel to the layer plane.

式中
−Ｘ−Ｙ−は、−ＣＯ−Ｏ−または−Ｏ−ＣＯ−である、
で表される環状ラクトンは、JP 2001-026 587 (A)に開示されている。これらの化合物は、広いスメクティック相により特徴づけられ、JP 2001-026 587 (A)における強誘電液晶混合物において用いるために提案されている。 formula

In the formula, —X—Y— is —CO—O— or —O—CO—.
JP 2001-026 587 (A) discloses a cyclic lactone represented by: These compounds are characterized by a broad smectic phase and have been proposed for use in ferroelectric liquid crystal mixtures in JP 2001-026 587 (A).

で表されるフッ素化フェナントレンおよび式

で表されるフッ素化９，１０−ジヒドロフェナントレンが開示されている。
これらはまた、広いスメクティック相を有し、同様に強誘電液晶混合物において用いるために提案されている。 U.S. Pat.No. 5,648,021 includes a formula

Fluorinated phenanthrene and formula

The fluorinated 9,10-dihydrophenanthrene represented by the formula is disclosed.
They also have a wide smectic phase and have been proposed for use in ferroelectric liquid crystal mixtures as well.

式中、
Ｌ^１およびＬ^２は、各々、互いに独立して、ＨまたはＦである、
で表されるフッ素化フェナントレンが提示されており、これらを、ネマティック液晶混合物において、特にＥＣＢディスプレイのために用いることが提案されている。Ｌ^１およびＬ^２が共にＨであり、１つのアルキル末端基および１つのアルコキシ末端基を含む例の化合物は、わずかにのみ負のΔεを有し、一方Ｌ^１およびＬ^２が共にＦであり、１つのアルコキシ末端基を含む例の化合物は、一層大きく負のΔεを有するが、一般的には、一層大きい回転粘度、顕著に低い溶解性およびさらにほとんどの場合において不適切なＵＶ安定性を有する。 DE 100 64 995 contains the formula

Where
L ¹ and L ² are each independently of each other H or F.
The fluorinated phenanthrenes represented by are proposed and have been proposed for use in nematic liquid crystal mixtures, especially for ECB displays. An example compound comprising L ¹ and L ² both H and containing one alkyl end group and one alkoxy end group has only a slightly negative Δε, while L ¹ and L ² are both F Example compounds containing one alkoxy end group have a larger negative Δε, but generally have greater rotational viscosity, significantly lower solubility, and in most cases inadequate UV stability. Have.

  Therefore, the demand for other mesogenic compounds and also especially good absolute value of dielectric anisotropy, value of optical anisotropy (Δn) corresponding to specific application, wide nematic phase, UV, heat and voltage It is clear that there is a need for both stability as well as liquid crystal media with negative dielectric anisotropy with low rotational viscosity.

式中、
Ｙは、−ＣＯ−、−ＣＳ−、−ＣＨ_２−、−ＣＦ_２−または−ＣＨＦ−、好ましくは−ＣＦ_２−であり、
Ｌ^１およびＬ^２は、各々、互いに独立して、Ｈ、Ｆ、Ｃｌまたは−ＣＮ、好ましくはＨまたはＦであり、好ましくはＬ^１およびＬ^２の少なくとも一方がＦであり、特に好ましくはＬ^１およびＬ^２は、共にＦであり、 This means that in the present invention the formula I

Where
Y is, -CO -, - CS -, - CH 2 -, - CF 2 - , or -CHF-, preferably -CF ₂ - a,
L ¹ and L ² are each independently of each other H, F, Cl or —CN, preferably H or F, preferably at least one of L ¹ and L ² is F, particularly preferably L ¹ and L ² are both F;

は、各々、互いに独立して、および１回よりも多く存在する場合には、また互いに独立して、
（ａ）さらに１つもしくは２つの隣接していないＣＨ_２基が、−Ｏ−および／または−Ｓ−により置換されていてもよい、トランス−１，４−シクロヘキシレン基、
（ｂ）１，４−シクロヘキセニレン基、
（ｃ）さらに１つもしくは２つの隣接していないＣＨ基が、Ｎにより置換されていてもよい、１，４−フェニレン基、または
（ｄ）１，４−ビシクロ［２．２．２］オクチレン、１，３−ビシクロ［１．１．１］ペンチレン、スピロ［３．３］ヘプタン−２，４−ジイル、ピペリジン−１，４−ジイル、ナフタレン−２，６−ジイル、デカヒドロナフタレン−２，６−ジイルおよび１，２，３，４−テトラヒドロナフタレン−２，６−ジイルからなる群から選択された基、
好ましくは

であり、

Are each independently of each other and, if present more than once, also independently of each other,
(A) a trans-1,4-cyclohexylene group, wherein one or two non-adjacent CH ₂ groups may be substituted by —O— and / or —S—;
(B) 1,4-cyclohexenylene group,
(C) 1,4-phenylene group, or (d) 1,4-bicyclo [2.2.2] octylene, wherein one or two non-adjacent CH groups may be substituted by N 1,3-bicyclo [1.1.1] pentylene, spiro [3.3] heptane-2,4-diyl, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2 A group selected from the group consisting of, 6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl;
Preferably

And

−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−または−Ｏ−ＣＯ−Ｏ−により置換されていてもよい、１〜１５個の炭素原子を有するアルキル基であり、
好ましくは、Ｒ^１およびＲ^２の１つは、１〜１２個の炭素原子を有するアルキルもしくはアルコキシ、２〜１２個の炭素原子を有するアルコキシアルキル、アルケニルもしくはアルケニルオキシであり、他方は、第１のものと独立して、同様に１〜１２個の炭素原子を有するアルキルもしくはアルコキシ、２〜１２個の炭素原子を有するアルコキシアルキル、アルケニルもしくはアルケニルオキシであるか、または、あるいはまた、Ｆ、Ｃｌ、Ｂｒ、−ＣＮ、−ＳＣＮ、−ＳＦ_５、−ＣＦ_３、−ＣＨＦ_２、−ＣＨ_２Ｆ、−ＯＣＦ_３もしくは−ＯＣＨＦ_２であり、 R ¹ and R ² are each independently of each other H, halogen, —CN, —SCN, —SF ₅ , —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ or CN or CF ₃ is monosubstituted or at least monosubstituted by halogen, wherein one or more CH ₂ groups are each independently of one another O or S atoms. -O-, -S-, -CH = CH-, -CF = CF-, -CF = CH-, -CH = CF-,

An alkyl group having 1 to 15 carbon atoms, optionally substituted by -CO-, -CO-O-, -O-CO- or -O-CO-O-;
Preferably ^one of R ¹ and R ² is alkyl or alkoxy having 1 to 12 carbon atoms, alkoxyalkyl, alkenyl or alkenyloxy having 2 to 12 carbon atoms, the other being the first Independently of alkyl or alkoxy having 1 to 12 carbon atoms, alkoxyalkyl, alkenyl or alkenyloxy having 2 to 12 carbon atoms, or alternatively F, Cl _{, Br, -CN, -SCN, -SF} 5, -CF 3, -CHF 2, -CH 2 F, a -OCF ₃ or -OCHF _2,

Z ¹ and ^{Z 2} are each, independently of one _{another, -CH 2 -CH 2 -, -} CF 2 -CF 2 -, - CF 2 -CH 2 -, - CH 2 -CF 2 -, - CH = CH —, —CF═CF—, —CF═CH—, —CH═CF—, —C≡C—, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O— , —OCF ₂ —, a single bond or a combination of two of these groups, wherein no two O atoms are bonded to each other;
_{Preferably, - (CH 2) 4 -} , - CH 2 -CH 2 -, - CF 2 -CF 2 -, - CH = CH -, - CF = CF -, - C≡C -, - CH 2 O- a _-CF 2 O-or a single bond,
Particularly _{preferably, -CH 2 O -, - CH} 2 -CH 2 -, - CF 2 -CF 2 -, - CF = CF -, - a _CF 2 O-or a single bond,

n and m are each 0, 1 or 2, where
n + m is 0, 1, 2 or 3, preferably 0, 1 or 2, particularly preferably 0 or 1,
Provided that when Y is —CO—, at least one of L ¹ and L ² is not H.
This is achieved by using a mesogenic compound represented by:

式中、パラメーターは、式Ｉの下に前に定義した通りであり、
Ｌ^１およびＬ^２は、好ましくは共にＦである、
で表される式Ｉで表される液晶化合物である。 Particular preference is given to subordinate formulas I-1 to I-3.

Where the parameters are as previously defined under formula I;
L ¹ and L ² are preferably both F,
A liquid crystal compound represented by the formula I represented by:

式中、パラメーターは、式Ｉについて定義した通りである、
で表される化合物からなる群から選択される。
Preference is given to compounds of the formula I, preferably selected from the group consisting of compounds of the formulas I-1 to I-3, in which the sum of n + m is 0 or 1, preferably 0. is there.
In certain embodiments, the compounds of the present invention have formula I-1a to I-3b

In which the parameters are as defined for formula I.
It is selected from the group consisting of compounds represented by:

が、

であり、
Ｚ^２が、好ましくは、−（ＣＨ_２）_４−、−ＣＨ_２−ＣＨ_２−、−ＣＦ_２−ＣＦ_２−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−Ｃ≡Ｃ−、−Ｏ−ＣＨ_２−、−Ｏ−ＣＦ_２−または単結合であり、
特に好ましくは、−Ｏ−ＣＨ_２−、−ＣＨ_２−ＣＨ_２−、−ＣＦ_２−ＣＦ_２−、−ＣＦ＝ＣＦ−、−Ｏ−ＣＦ_２−または単結合であり、
Ｌ^１、Ｌ^２、Ｒ^１およびＲ^２が、式Ｉの下に上記で定義した通りであり、Ｌ^１およびＬ^２が、好ましくは共にＦである化合物により表される。 A preferred embodiment is represented by Formula I, wherein the total n + m is 1,
m or n is 1,

But,

And
Z ² is _{preferably, - (CH 2) 4 -} , - CH 2 -CH 2 -, - CF 2 -CF 2 -, - CH = CH -, - CF = CF -, - C≡C -, - O—CH ₂ —, —O—CF ₂ — or a single bond,
Particularly _{preferably, -O-CH 2 -, -} CH 2 -CH 2 -, - CF 2 -CF 2 -, - CF = CF -, - or a single bond, - O-CF ₂
L ¹ , L ² , R ¹ and R ² are represented by compounds as defined above under formula I, and L ¹ and L ² are preferably both F.

Particularly preferred is preferably represented by formulas I-1 to I-3, where n and m are both 0,
A formula selected from the group consisting of compounds wherein L ¹ , L ² , R ¹ and R ² are as defined above under the corresponding formula, and L ¹ and L ² are preferably both F A compound represented by I.

Compounds of formula I containing branched wing groups R ¹ and / or R ² are sometimes due to better solubility in conventional liquid crystal base materials, but they are optically active. In some cases, it can be important, especially as a chiral dopant. This type of smectic compound is suitable as a component of a ferroelectric material. The compounds of the formula I having the S _A phase are suitable, for example, for thermally addressed displays.

When R ¹ and / or R ² is an alkyl group and / or an alkoxy group, this may be linear or branched. It is preferably straight-chain and has 2, 3, 4, 5, 6 or 7 carbon atoms and is therefore preferably ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethoxy, Propoxy, butoxy, pentoxy, hexyloxy or heptyloxy, plus methyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy Or tetradecyloxy.

  Oxaalkyl or alkoxyalkyl is preferably linear 2-oxapropyl (= methoxymethyl), 2-(= ethoxymethyl) or 3-oxabutyl (= 2-methoxyethyl), 2-, 3- or 4- Oxapentyl, 2-, 3-, 4- or 5-oxahexyl, 2-, 3-, 4-, 5- or 6-oxaheptyl, 2-, 3-, 4-, 5-, 6- or 7 -Oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl or 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-oxadecyl It is.

When R ¹ and / or R ² is an alkyl group in which one CH ₂ group is substituted by —CH═CH—, this may be straight-chain or branched Good. This is preferably straight-chain and has 2 to 10 carbon atoms. This is therefore especially the case for vinyl, prop-1- or -2-enyl, but-1-, -2- or -3-enyl, pent-1-, -2-, -3- or -4-enyl. Hex-1-, -2-, -3-, -4- or -5-enyl, hept-1-, -2-, -3-, -4-, -5- or -6-enyl, oct -1-, -2-, -3-, -4-, -5, -6 or -7-enyl, non-1-, -2-, -3-, -4-, -5, -6, -7- or -8-enyl or dec-1-, -2-, -3-, -4-, -5, -6, -7-, -8- or -9-enyl It is.

When R ¹ and / or R ² are alkyl groups in which one CH ₂ group is substituted by —O— and one is substituted by —CO—, these are preferably adjacent Yes. They therefore contain an acyloxy group —CO—O— or an oxycarbonyl group —O—CO—. These are preferably straight-chain and have 2 to 6 carbon atoms. Thus, these are in particular acetoxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy, acetoxymethyl, propionyloxymethyl, butyryloxymethyl, pentanoyloxymethyl, 2-acetoxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 3-acetoxypropyl, 3-propionyloxypropyl, 4-acetoxybutyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl , Butoxycarbonylmethyl, 2- (methoxycarbonyl) ethyl, 2- (ethoxycarbonyl) ethyl, 2- (propoxycarbonyl) Chill, 3- (methoxycarbonyl) propyl, 3- (ethoxycarbonyl) propyl or 4- (methoxycarbonyl) butyl.

R ¹ and / or R ² has one CH ₂ group unsubstituted or substituted with —CH═CH— and the adjacent CH ₂ group substituted with CO or CO—O or O—CO If it is an alkyl group, it may be linear or branched. This is preferably straight-chain and has 4 to 13 carbon atoms. Thus, this is especially true for acryloyloxymethyl, 2-acryloyloxyethyl, 3-acryloyloxypropyl, 4-acryloyloxybutyl, 5-acryloyloxypentyl, 6-acryloyloxyhexyl, 7-acryloyloxyheptyl, 8-acryloyl. Oxyoctyl, 9-acryloyloxynonyl, 10-acryloyloxydecyl, methacryloyloxymethyl, 2-methacryloyloxyethyl, 3-methacryloyloxypropyl, 4-methacryloyloxybutyl, 5-methacryloyloxypentyl, 6-methacryloyloxyhexyl, 7 -Methacryloyloxyheptyl, 8-methacryloyloxyoctyl or 9-methacryloyloxynonyl.

When R ¹ and / or R ² is an alkyl or alkenyl group that is monosubstituted by CN or CF ₃ , this group is preferably linear. Substitution with CN or CF ₃ is at any desired position.

When R ¹ and / or R ² is an alkyl or alkenyl group that is at least monosubstituted by halogen, this group is preferably straight-chain and the halogen is preferably F or Cl. In the case of polysubstitution, the halogen is preferably F. The resulting group also contains a perfluoro group. In the case of monosubstitution, the fluorine or chlorine substituent can be at any desired position, but is preferably at the ω position.

Branched groups generally contain no more than one chain branch. Preferred branched groups R ¹ are isopropyl, 2-butyl (= 1-methylpropyl), isobutyl (= 2-methylpropyl), 2-methylbutyl, isopentyl (= 3-methylbutyl), 2-methylpentyl, 3- Methylpentyl, 2-ethylhexyl, 2-propylpentyl, isopropoxy, 2-methylpropoxy, 2-methylbutoxy, 3-methylbutoxy, 2-methylpentoxy, 3-methylpentoxy, 2-ethylhexyloxy, 1-methyl Hexyloxy and 1-methylheptyloxy.

When R ¹ and / or R ² is an alkyl group in which two or more CH ₂ groups are substituted by —O— and / or —CO—O—, this is linear Or it may be branched. This is preferably branched and has 3 to 12 carbon atoms. Thus, this is especially true for biscarboxymethyl, 2,2-biscarboxyethyl, 3,3-biscarboxypropyl, 4,4-biscarboxybutyl, 5,5-biscarboxypentyl, 6,6-biscarboxyhexyl. 7,7-biscarboxyheptyl, 8,8-biscarboxyoctyl, 9,9-biscarboxynonyl, 10,10-biscarboxydecyl, bis (methoxycarbonyl) methyl, 2,2-bis (methoxycarbonyl) ethyl 3,3-bis (methoxycarbonyl) propyl, 4,4-bis (methoxycarbonyl) butyl, 5,5-bis (methoxycarbonyl) pentyl, 6,6-bis (methoxycarbonyl) hexyl, 7,7-bis (Methoxycarbonyl) heptyl, 8,8-bis (methoxycarbonyl) octyl, Sus (ethoxycarbonyl) methyl, 2,2-bis (ethoxycarbonyl) ethyl, 3,3-bis (ethoxycarbonyl) propyl, 4,4-bis (ethoxycarbonyl) butyl or 5,5-bis (ethoxycarbonyl) hexyl It is.

Particularly preferred is the formula I, wherein n = 0 or 1, m = 0, and R ¹ is methyl, ethyl, propyl, butyl, pentyl, vinyl, 1E-propenyl, 1E-butenyl. Or a compound containing 1E-pentenyl and a medium containing these compounds. Of these compounds, alkyl-substituted compounds are particularly preferably used.
The compounds of formula I are prepared according to the following schemes (Schemes I to XX).

  Cyclic lactones can be prepared by a Ullmann type coupling reaction according to scheme I by intramolecular cyclization of halogenated arylphenyl esters in a suitable manner (Houben Weyl, Methoden der Organischen Chemie [ Organic Chemistry Method], New York, 1993). Alternatively, they can be obtained by an intramolecular cross-coupling reaction catalyzed by palladium, as shown in Scheme II and Scheme III.

式中、スキームＩａ〜Ｉｄ、ＩＩ、ＩＩＩ、ＩＩＩａ、ＩＶ〜ＸＸと同様にして、他に明白に述べない限り、
ＲおよびＲ’は、各々、互いに独立して、式Ｉの下に

について上記で定義した通りであり、
Ｈａｌは、ハロゲン、好ましくはＢｒまたはＩである。
Ａ：Hasan, I. et al., Chem. Rev. (2002), 102, １３５９〜１４６９頁、
Ｂ：Hennings, D.D. et al., Org. Lett. (1999), 1, １２０５〜１２０８頁。 Alternatively, as shown in Scheme IIIa, using the example of the Negishi reaction, cross-coupling is also carried out in the first step with correspondingly protected phenols and carboxylic esters. (Negishi, E. et al., J. Org. Chem. (1977) 42, 1821-1823).
Scheme I

Wherein, as in Schemes Ia-Id, II, III, IIIa, IV-XX, unless explicitly stated otherwise,
R and R ′ are each independently of one another under formula I

As defined above, and
Hal is halogen, preferably Br or I.
A: Hasan, I. et al., Chem. Rev. (2002), 102, pages 1359 to 1469,
B: Hennings, DD et al., Org. Lett. (1999), 1, 1205-1208.

The ester precursor is obtained by standard reaction (Houben-Weyl) from commercially available 4-bromo-3-fluoro-1-iodobenzene or (if R = methyl, 4-bromo- Synthesize 2-fluorotoluene or 4-bromo-2-fluorophenol (from ABCR, Karlsruhe, Germany).
The alkyl side chain is advantageously introduced into the precursor by Sonogashira coupling, as shown in Scheme Ia.
Precursors containing alkoxy side chains are advantageously obtained according to Scheme Ib.

  The two types of intermediates obtained according to Scheme Ia or Ib can be converted to either phenol or carboxylic acid and then esterified as shown in Scheme Ic by way of example for alkyl compounds.

Scheme Ia

Scheme Ib

Scheme Ic

スキームＩＩ

Ｃ：Bringmann, G. et al., Org. Synth. (2002), 79, ７２〜８３頁。
スキームＩＩＩ

Ｄ：Alo, B.I. et al., J. Org. Chem. (1991), 56, ３７６３〜３７６８頁。 Bromophenol can be protected and converted to boronic acid according to Scheme Id for subsequent Suzuki coupling.
Scheme Id

Scheme II

C: Bringmann, G. et al., Org. Synth. (2002), 79, 72-83.
Scheme III

D: Alo, BI et al., J. Org. Chem. (1991), 56, 3763-3768.

  Lactones (1a) can be converted to benzochromenes (1b), or alternatively using Lawesson's reagents, as in EP 1 061 113, as shown in Scheme IV, followed by DAST. The reaction can be converted to difluorobenzochromenes (1c) (Bunelle, WH et al., J. Org. Chem. (1990), 55, pp. 768-770).

Alternatively, lactones (1a) are reacted with LiAlH ₄ in THF according to Scheme V (Ringom, R. and Bennecke, T., Acta. Chem. Scand. (1999), 53, 41-47). Then, it can be reacted with DAST to obtain fluorobenzochromenes (1d).

  The aforementioned alternative synthesis, in which cross-coupling is carried out in the first step with correspondingly protected phenols and carboxylic esters, is shown in Scheme IIIa on page 16 using an example of the Negi reaction.

式中、
ＰＧは、保護基であり、
Ｘは、ハロゲン、好ましくはＢｒであり、
Ｘ^１およびＸ^２は、互いに独立して、ハロゲンであり、
Ｘ^１は、好ましくはＣｌ、ＢｒまたはＩ、特に好ましくはＢｒまたはＩ、極めて特に好ましくはＢｒであり、
Ｒ”は、アルキル、好ましくはメチルであり、
ＲおよびＲ’は、各々、互いに独立して、スキームＩについて上記で定義した通りである。 Scheme IIIa

Where
PG is a protecting group,
X is halogen, preferably Br,
X ¹ and X ² are independently of one another halogen,
X ¹ is preferably Cl, Br or I, particularly preferably Br or I, very particularly preferably Br;
R ″ is alkyl, preferably methyl,
R and R ′ are each independently as defined above for Scheme I.

スキームＶ

After removal of the protecting group, the lactone can be obtained, for example, by simply heating in an inert solvent or by treatment with an acid or base.
Scheme IV

Scheme V

がＲ^１、Ｒ^２、

であり、ここで、

環がまた複素環式環であってもよい化合物を、スキームＶＩ〜ＸＸに従って得ることができる。 Represented by formula I, wherein

Are R ¹ , R ² ,

And where

Compounds where the ring may also be a heterocyclic ring can be obtained according to Schemes VI-XX.

Scheme VI

Scheme VII

Scheme VIII

Scheme IX

  4-Bromo-3-fluoro-1-iodobenzene and 4-bromo-2-fluorophenol can be similarly converted to the corresponding target compounds in a manner similar to the reaction sequences shown in Schemes I-V. Suitable as a synthetic component for the derivatives of

Cyclohexyl derivatives are obtained, for example, according to Scheme X. Metallation of 4-bromo-3-fluoro-1-iodobenzene with n-butyllithium and addition onto cyclohexanones gives phenylcyclohexanols from which 4-bromo-2- A fluoro-1-cyclohexylbenzene derivative is obtained after water removal and hydrogenation.
Scheme X

Aryl derivatives are obtained, for example, according to Scheme XI. Direct Suzuki coupling of 4-bromo-3-fluoro-1-iodobenzene with the corresponding boronic acid allows the preparation of 1-aryl-4-bromo-2-fluoro derivatives.
Scheme XI

スキームＸＩＩＩ

Sonogashira coupling of 4-bromo-3-fluoro-1-iodobenzene with phenylacetylenes gives 4-bromo-2-fluorotolane as shown in Scheme XII. These can be hydrogenated to give ethylene bridged compounds as shown in Scheme XIII or converted to diketones by the method of VO Rogatchov, VD Filimonov, MS Yusubov, Synthesis (2001), 7, 1001-1003. From this, a tetrafluoroethylene crosslinking compound can be obtained by reaction with sulfur tetrafluoride.
Scheme XII

Scheme XIII

  From 4-bromo-2-fluorophenol, hydroxyl compounds and triflates can be obtained as synthetic components according to Scheme XIV. 4-Bromo-2-fluorophenol is now protected with a suitable protecting group “PG” (eg benzyl); the corresponding reaction according to Schemes IV and subsequent removal of the protecting group (eg benzyl as PG) Can be prepared by phenols and triflates (trifluoromethanesulfonic acids, TfO-) from them.

式中、スキームＸＶ〜ＸＸにおけるように、
Ｇは、Ｙ−ＯまたはＯ−Ｙであり、
Ｙは、式Ｉの下に上記で定義した通りである。 Scheme XIV

Where, as in Schemes XV-XX,
G is YO or OY,
Y is as defined above under Formula I.

式中、Ｒは、スキームＸＶＩ〜ＸＸと同様に、式Ｉの下にＲ^１について定義した通りである。 The phenols thus obtained can be converted to esters and ethers according to Scheme XV.
Scheme XV

In which R is as defined for R ¹ under Formula I, as in Schemes XVI-XX.

CF ₂ O bridging compounds are obtained according to WO 02/48 073 and WO 01/64 667 as shown in Scheme XVI.
Scheme XVI

Preparation of stilbenes is possible by Suzuki coupling of triflates obtained according to Scheme XIV with etheneboronic acid (Scheme XVII).
Scheme XVII

Difluorostilbenes are likewise available via the Stille reaction as described by L. Lu, DJ Burton, Tetrahedron Lett. 1997, 38, 7673-7676 (Scheme XVIII).
Scheme XVIII

Carboxylation of triflates by the method of S. Cacchi, PG Ciattini, E. Morera, G. Ortar, Tetrahedron Lett. (1986), 27, 3931-3934 provides carboxylic acid esters (Scheme XIX). After saponification to the corresponding carboxylic acids, for example, phenyl esters can be prepared by reaction with the phenols.
Scheme XIX

Carboxylic acid esters obtained according to Scheme XIX can be converted to difluorobenzyl ethers according to WO 02/480 73 and WO 01/64 667 as shown in Scheme XX.
Scheme XX

Examples of the structures of preferred compounds of the formula I, in which R and R ′ have the respective meanings indicated for R ¹ and R ² respectively under formula I are given on the following pages.

  The liquid crystal medium of the present invention contains one or more compounds represented by Formula I.

式中、
Ｙは、−ＣＯ−、−ＣＳ−、−ＣＨ_２−、−ＣＦ_２−または−ＣＨＦ−、好ましくは−ＣＦ_２−であり、
Ｌ^１およびＬ^２は、各々、互いに独立して、Ｈ、Ｆ、Ｃｌまたは−ＣＮ、好ましくはＨまたはＦであり、好ましくはＬ^１およびＬ^２の少なくとも一方がＦであり、特に好ましくはＬ^１およびＬ^２は、共にＦであり、 In a preferred embodiment, the liquid crystal medium of the present invention includes the following.
a) Formula I

Where
Y is, -CO -, - CS -, - CH 2 -, - CF 2 - , or -CHF-, preferably -CF ₂ - a,
L ¹ and L ² are each independently of each other H, F, Cl or —CN, preferably H or F, preferably at least one of L ¹ and L ² is F, particularly preferably L ¹ and L ² are both F;

は、各々、互いに独立して、および１回よりも多く存在する場合には、また互いに独立して、
（ａ）さらに１つもしくは２つの隣接していないＣＨ_２基が、−Ｏ−および／または−Ｓ−により置換されていてもよい、トランス−１，４−シクロヘキシレン基、
（ｂ）１，４−シクロヘキセニレン基、
（ｃ）さらに１つもしくは２つの隣接していないＣＨ基が、Ｎにより置換されていてもよい、１，４−フェニレン基、または
（ｄ）１，４−ビシクロ［２．２．２］オクチレン、１，３−ビシクロ［１．１．１］ペンチレン、スピロ［３．３］ヘプタン−２，４−ジイル、ピペリジン−１，４−ジイル、ナフタレン−２，６−ジイル、デカヒドロナフタレン−２，６−ジイルおよび１，２，３，４−テトラヒドロナフタレン−２，６−ジイルからなる群から選択された基、
好ましくは

であり、

Are each independently of each other and, if present more than once, also independently of each other,
(A) a trans-1,4-cyclohexylene group, wherein one or two non-adjacent CH ₂ groups may be substituted by —O— and / or —S—;
(B) 1,4-cyclohexenylene group,
(C) 1,4-phenylene group, or (d) 1,4-bicyclo [2.2.2] octylene, wherein one or two non-adjacent CH groups may be substituted by N 1,3-bicyclo [1.1.1] pentylene, spiro [3.3] heptane-2,4-diyl, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2 A group selected from the group consisting of, 6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl;
Preferably

And

−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−または−Ｏ−ＣＯ−Ｏ−により置換されていてもよい、１〜１５個の炭素原子を有するアルキル基であり、
好ましくは、Ｒ^１およびＲ^２の１つは、１〜１２個の炭素原子を有するアルキルもしくはアルコキシ、２〜１２個の炭素原子を有するアルコキシアルキル、アルケニルもしくはアルケニルオキシであり、他方は、第１のものと独立して、同様に１〜１２個の炭素原子を有するアルキルもしくはアルコキシ、２〜１２個の炭素原子を有するアルコキシアルキル、アルケニルもしくはアルケニルオキシであるか、または、あるいはまた、Ｆ、Ｃｌ、Ｂｒ、−ＣＮ、−ＳＣＮ、−ＳＦ_５、−ＣＦ_３、−ＣＨＦ_２、−ＣＨ_２Ｆ、−ＯＣＦ_３もしくは−ＯＣＨＦ_２であり、 R ¹ and R ² are each independently of each other H, halogen, —CN, —SCN, —SF ₅ , —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ or CN or CF ₃ is monosubstituted or at least monosubstituted by halogen, wherein one or more CH ₂ groups are each independently of one another O or S atoms. -O-, -S-, -CH = CH-, -CF = CF-, -CF = CH-, -CH = CF-,

An alkyl group having 1 to 15 carbon atoms, optionally substituted by -CO-, -CO-O-, -O-CO- or -O-CO-O-;
Preferably ^one of R ¹ and R ² is alkyl or alkoxy having 1 to 12 carbon atoms, alkoxyalkyl, alkenyl or alkenyloxy having 2 to 12 carbon atoms, the other being the first Independently of alkyl or alkoxy having 1 to 12 carbon atoms, alkoxyalkyl, alkenyl or alkenyloxy having 2 to 12 carbon atoms, or alternatively F, Cl _{, Br, -CN, -SCN, -SF} 5, -CF 3, -CHF 2, -CH 2 F, a -OCF ₃ or -OCHF _2,

Z ¹ and ^{Z 2} are each, independently of one _{another, -CH 2 -CH 2 -, -} CF 2 -CF 2 -, - CF 2 -CH 2 -, - CH 2 -CF 2 -, - CH = CH —, —CF═CF—, —CF═CH—, —CH═CF—, —C≡C—, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O— , —OCF ₂ —, a single bond or a combination of two of these groups, wherein no two O atoms are bonded to each other;
_{Preferably, - (CH 2) 4 -} , - CH 2 -CH 2 -, - CF 2 -CF 2 -, - CH = CH -, - CF = CF -, - C≡C -, - CH 2 O- a _-CF 2 O-or a single bond,
Particularly _{preferably, -CH 2 O -, - CH} 2 -CH 2 -, - CF 2 -CF 2 -, - CF = CF -, - a _CF 2 O-or a single bond,

n and m are each 0, 1 or 2, where
n + m is 0, 1, 2 or 3, preferably 0, 1 or 2, particularly preferably 0 or 1.
One or more dielectrically negative compounds represented by:

式中、
Ｒ^２１およびＲ^２２は、各々、互いに独立して、式Ｉの下でＲ^１について上記で定義した通りであり、
Ｚ^２１およびＺ^２２は、各々、互いに独立して、式Ｉの下でＺ^１について上記で定義した通りであり、 b) Formula II

Where
R ²¹ and R ²² are each, independently of one another, as defined above for R ¹ under Formula I;
Z ²¹ and Z ²² are each independently of one another as defined above for Z ¹ under Formula I;

好ましくは

は、

であり、他方は、各々、互いに独立して、

好ましくは

であり、 At least one of the existing rings

Preferably

Is

And the other is independently of each other,

Preferably

And

は、

であり、

は、存在する場合には、

であり、
極めて特に好ましくは、

および存在する場合には、

の１つは、

好ましくは

であり、 Particularly preferably,

Is

And

If present,

And
Very particularly preferably,

And if present,

One of the

Preferably

And

は、各々、互いに独立して、

であり、

は、

であり、
Ｌ^２１およびＬ^２２は、共にＣ−Ｆであるか、または２つのうちの一方がＮであり、他方がＣ−Ｆであり、好ましくは共にＣ−Ｆであり、
ｌは、０、１または２、好ましくは０または１である、
で表される１種または２種以上の誘電的に負の化合物；
並びに随意に
Or

Are independent of each other,

And

Is

And
L ²¹ and L ²² are both C—F, or one of the two is N, the other is C—F, preferably both C—F,
l is 0, 1 or 2, preferably 0 or 1.
One or more dielectrically negative compounds represented by:
And optionally

式中、
Ｒ^３１およびＲ^３２は、各々、互いに独立して、式Ｉの下でＲ^１について上記で定義した通りであり、
Ｚ^３１、Ｚ^３２およびＺ^３３は、各々、互いに独立して、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−ＣＯＯ−または単結合であり、

は、各々、互いに独立して、

であり、
ｏおよびｐは、互いに独立して、０または１であり、 c) Formula III

Where
R ³¹ and R ³² are each independently of one another as defined above for R ¹ under Formula I;
Z ³¹ , Z ³² and Z ³³ are each independently of each other —CH ₂ CH ₂ —, —CH═CH—, —COO— or a single bond,

Are independent of each other,

And
o and p are independently of each other 0 or 1,

は、各々、互いに独立して、

であり、 But preferably,
R ³¹ and R ³² are each independently of one another alkyl or alkoxy having 1 to 5 carbon atoms or alkenyl having 2 to 5 carbon atoms;

Are independent of each other,

And

であり、
ここで、極めて特に好ましくは、２つの隣接する環、好ましくは

は、直接結合している、
で表される１種または２種以上の誘電的に中性の化合物。 Very particularly preferably, at least two of these rings are

And
Here, very particularly preferably, two adjacent rings, preferably

Is directly bound,
One or two or more dielectrically neutral compounds represented by:

が直接結合している、１種または２種以上の化合物を含む。 The liquid crystal medium preferably contains one or more compounds of the formula I that do not contain biphenyl units.
The liquid crystal medium is particularly preferably represented by the formula I
In which two adjacent rings, preferably

Includes one or more compounds to which are directly attached.

  In a preferred embodiment, which may be identical to the embodiment just described, the liquid crystal medium comprises one or more compounds selected from the group consisting of compounds of formula I-3.

式中、
Ｒ^２１、Ｒ^２２、Ｚ^２１、Ｚ^２２、

およびｌは、各々、式ＩＩの下に上記で定義した通りである。Ｒ^２１は、好ましくは、好ましくは１〜５個の炭素原子を有するアルキルであり、Ｒ^２１は、好ましくは、好ましくは各々１〜５個の炭素原子を有するアルキルまたはアルコキシであり、Ｚ^２２およびＺ^２１は、存在する場合には、好ましくは単結合である。 The liquid crystal medium preferably contains one or more compounds selected from the group consisting of compounds represented by Formulas II-1 to II-3.

Where
R ²¹ , R ²² , Z ²¹ , Z ²² ,

And l are each as defined above under Formula II. R ²¹ is preferably alkyl having preferably 1 to 5 carbon atoms, R ²¹ is preferably alkyl or alkoxy, preferably each having 1 to 5 carbon atoms, Z ²² and Z ²¹ , when present, is preferably a single bond.

式中、Ｒ^３１、Ｒ^３２、Ｚ^３１、Ｚ^３２、

は、各々、式ＩＩＩの下に上記で定義した通りである、
で表される化合物からなる群から選択された１種または２種以上の化合物を含む。 The liquid crystal medium is particularly preferably of formula III-1 to III-3:

In the formula, R ³¹ , R ³² , Z ³¹ , Z ³² ,

Are each as defined above under Formula III.
1 type or 2 or more types of compounds selected from the group which consists of a compound represented by these are included.

式中、ｎおよびｍは、各々、互いに独立して、１〜５であり、ｏおよびｐは、各々、これらの両方に、および互いに独立して、０〜３である、 The liquid crystal medium is particularly preferably of formulas III-1a to III-1d, III-1e, III-2a to III-2g and III-3a to III-3d:

Wherein n and m are each independently 1 to 5, and o and p are each both of them and independently of each other, 0 to 3.

式中、Ｒ^３１およびＲ^３２は、各々、式ＩＩＩの下に上記で定義した通りであり、好ましくは、式ＩＩＩ−１の下に上記で定義した通りであり、特に化合物ＩＩＩ−２ｇおよびＩＩＩ−３ｃにおけるフェニル環は、随意に、フッ素化されていてもよく、しかし化合物が、式ＩＩおよびこの従属式で表される化合物と同一であるようにではない、
で表される化合物からなる群から選択された１種または２種以上の化合物を含む。Ｒ^３１は、好ましくは、１〜５個の炭素原子を有する、特に好ましくは１〜３個の炭素原子を有するｎ−アルキルであり、Ｒ^３２は、好ましくは、１〜５個の炭素原子を有するｎ−アルキルもしくはｎ−アルコキシまたは２〜５個の炭素原子を有するアルケニルである。これらの中で、特に好ましいのは、式ＩＩＩ−１ａ〜ＩＩＩ−１ｄで表される化合物である。

In which R ³¹ and R ³² are each as defined above under formula III, preferably as defined above under formula III-1, in particular compounds III-2g and III The phenyl ring in -3c may optionally be fluorinated, but not so that the compound is identical to the compound of formula II and this subordinate formula;
1 type or 2 or more types of compounds selected from the group which consists of a compound represented by these are included. R ³¹ is preferably n-alkyl having 1 to 5 carbon atoms, particularly preferably 1 to 3 carbon atoms, and R ³² is preferably 1 to 5 carbon atoms. N-alkyl or n-alkoxy or alkenyl having 2 to 5 carbon atoms. Of these, compounds represented by the formulas III-1a to III-1d are particularly preferable.

式中、Ｒ^３１およびＲ^３３は、各々、式ＩＩＩの下に上記で定義した通りであり、好ましくは、式ＩＩＩ−２ｇまたはＩＩＩ−３ｃの下に上記で定義した通りである、
で表される化合物である。 Preferred fluorinated compounds of formula III-2g and III-3c are formulas III-2g ′ and III-3c ′.

In which R ³¹ and R ³³ are each as defined above under formula III, preferably as defined above under formula III-2g or III-3c.
It is a compound represented by these.

  In this application, unless expressly stated otherwise, the term compound is taken to mean both a compound and a plurality of compounds.

The liquid-crystalline media of the invention preferably have a nematic phase in each case of at least −20 ° C. to 80 ° C., preferably −30 ° C. to 85 ° C. and very particularly preferably −40 ° C. to 100 ° C. The term “having a nematic phase” means here that first the smectic phase and crystallization are not observed at low temperatures at the corresponding temperature, and secondly, no clearing occurs when heating from the nematic phase. To be interpreted. Inspection at low temperature is performed in a flow viscometer at the corresponding temperature and checked by storage in a test cell having a layer thickness corresponding to the electro-optical application for at least 100 hours. The storage stability ( _tstore (T)) at the corresponding temperature (T) is presented as the time until all three test cells show no change. At high temperatures, the clearing point is measured in the capillaries by conventional methods.
Furthermore, the liquid crystal medium of the present invention is characterized by a low optical anisotropy value.

  The term “alkyl” preferably includes straight-chain and branched alkyl groups having 1 to 7 carbon atoms, in particular the straight-chain groups methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl. . Groups having 2 to 5 carbon atoms are generally preferred.

The term “alkenyl” preferably includes straight-chain and branched alkenyl groups having 2-7 carbon atoms, especially straight-chain groups. Particularly preferred alkenyl _groups, C _{2 ~C} 7 -1E- _alkenyl, C _{4 ~C} 7 -3E- _alkenyl, C _{5 ~C} 7 -4- _alkenyl, C _{6 ~C} 7 -5- alkenyl and _C 7 -6 - alkenyl, in particular _C 2 _{-C 7-1E-alkenyl,} C ₄ -C 7 -3E-alkenyl and _C 5 _-C 7-4-alkenyl. Examples of more preferred alkenyl groups are vinyl, 1E-propenyl, 1E-butenyl, 1E-pentenyl, 1E-hexenyl, 1E-heptenyl, 3-butenyl, 3E-pentenyl, 3E-hexenyl, 3E-heptenyl, 4-pentenyl, 4Z-hexenyl, 4E-hexenyl, 4Z-heptenyl, 5-hexenyl, 6-heptenyl and the like. Groups having up to 5 carbon atoms are generally preferred.

The term “fluoroalkyl” is preferably a linear group with a terminal fluorine, ie fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl and 7 -Includes fluoroheptyl. However, fluorine at other positions is not excluded.
The term “oxaalkyl” or “alkoxyalkyl” is preferably represented by the formula C _n H _{2n + 1} —O— (CH ₂ ) _m , wherein n and m are each independently of each other 1 to A linear group which is 6. n is preferably 1, and m is preferably 1-6.

  Compounds containing vinyl end groups and compounds containing methyl end groups have a low rotational viscosity.

  In this application, the term dielectrically positive compound means a compound having a Δε of> 1.5, and a dielectrically neutral compound is a compound where −1.5 ≦ Δε ≦ 1.5. As used herein, a dielectrically negative compound means a compound having a Δε of <−1.5. The dielectric anisotropy of the compound, here at least one test in which 10% of the compound is dissolved in a liquid crystal host and the capacitance of this mixture is 1 kHz, with a homeotropic surface orientation and a layer thickness of about 20 μm By determining in the cell and at least one test cell having a uniform surface orientation and a layer thickness of about 20 μm. The measured voltage is typically between 0.5V and 1.0V, but is always lower than the capacitive threshold of the respective liquid crystal mixture.

  The host mixture used to determine the applicationally relevant physical parameters is ZLI-4792 from Merck KGaA, Germany. As an exception, the determination of the dielectric anisotropy of dielectrically negative compounds is likewise carried out using ZLI-2857 from Merck KGaA, Germany. The value for each compound to be tested is obtained from properties such as the change in the dielectric constant of the host mixture after addition of the compound to be tested and extrapolation to 100% of the compound used.

  The concentration used for the compound to be tested is 10%. If the solubility of the compound to be examined is inadequate for this purpose, the concentration used is the exception, until the concentration is below the solubility limit, ie 5%, 2.5 %.

The term threshold voltage usually relates to the optical threshold for 10% relative contrast (V ₁₀ ). However, in the context of liquid crystal mixtures having negative dielectric anisotropy, the term threshold voltage is also referred to as the Fredericks threshold in this application, unless explicitly stated otherwise. Used for the threshold voltage (V ₀ ).

  All concentrations in this application are expressed in weight percent and relate to the corresponding mixture as a whole, unless explicitly stated otherwise. All physical properties were determined and determined in accordance with "Merck Liquid Crystals, Physical Properties of Liquid Crystals", November 1997 situation, Merck KGaA, Germany, and unless stated otherwise, 20 ° C It corresponds to the temperature. Δn is determined at 589 nm and Δε is determined at 1 kHz.

In the case of a liquid crystal medium having negative dielectric anisotropy, the threshold voltage was determined as the capacitive threshold V ₀ in a cell having a liquid crystal layer homeotropically aligned with lecithin.

  The liquid crystal media of the present invention can contain other additives and optionally also chiral dopants in conventional amounts, if desired. The total amount of these additives used is 0% to 10%, preferably 0.1% to 6%, based on the total amount of the mixture. The concentration of the individual compounds used is preferably 0.1 to 3% in each case. The concentrations of these and similar additives are not taken into account when indicating the concentration and concentration range of the liquid crystal compound in the liquid crystal medium.

  The composition consists of a plurality of compounds, preferably 3-30, particularly preferably 6-20 and very particularly preferably 10-16, which are mixed in a conventional manner. In general, the desired amount of the components used in the lesser amount is dissolved in the components making up the principal constituent, preferably at elevated temperature. Completion of the dissolution process is particularly easy to observe if the selected temperature is higher than the clearing point of the main component. However, it is also possible to prepare the liquid-crystal mixture in other customary ways, for example using a premix or from a so-called “multibottle” system.

  With suitable additives, the liquid crystal phases of the invention can be modified so that they can be used in all types of displays, and in particular in the ECB and IPS displays previously disclosed.

  The following examples have the effect of illustrating the present invention without representing limitations. In the example, the melting point T (C, N) of the liquid crystal material, the transition T (S, N) from the smectic (S) phase to the nematic (N) phase, and the clearing point T (N, I) are shown in degrees Celsius. Different smectic phases are characterized by corresponding subscripts.

Percentages herein are percentages by weight, unless expressly stated otherwise, and physical properties are values at 20 ° C., unless expressly stated otherwise.
All temperature values given in this application are in degrees Centigrade, and all temperature differences are correspondingly degrees of difference, unless explicitly stated otherwise.

In the synthesis examples and schemes, the abbreviations have the following meanings:
BuLi n-butyllithium,
DAST diethylaminosulfur trifluoride,
DCC dicyclohexylcarbodiimide,
DMAP dimethylaminopyridine,
DMF N, N-dimethylformamide,
dppf 1,1′-bis (diphenylphosphino) ferrocene,
dppp 1,3-bis (diphenylphosphino) propane,
LDA lithium diisopropylamide,
MBT MBT ether, methyl tert-butyl ether and THF tetrahydrofuran.

In this application and in the following examples, the structure of the liquid crystal compound is indicated by an acronym and its conversion to the chemical formula is obtained according to the following Tables A and B All groups C _n H _{2n + 1} and C _m H _{2m + 1} are linear alkyl groups having n and m carbon atoms, respectively. The codes in Table B are self explanatory. In Table A, only the initial letter relating to the basic structure is shown. In each case, the codes for the substituents R ¹ , R ² , L ¹ , L ² and L ³ are shown after the initial letters relating to the basic structure, separated by a hyphen:

Table A:

Table B:

Examples The following examples are intended to illustrate the invention without limiting it. In the present specification, the percentage is weight percent. All temperatures are given in degrees Celsius. Δn represents optical anisotropy (589 nm, 20 ° C.), Δε represents dielectric anisotropy (1 kHz, 20 ° C.), R. Indicates the voltage holding ratio (1 V after 5 minutes in the oven at 100 ° C.). V ₁₀ , V ₅₀ and V ₉₀ (threshold voltage, mid-grey voltage and saturation voltage, respectively) and V ₀ (capacitive threshold voltage) were each determined at 20 ° C.

１９０ｇ（０．６００ｍｏｌ）の４−ブロモ−２−フルオロ−１−ヨードベンゼンおよび６５．３ｍｌの１−ペンチンを、９００ｍｌのＴＨＦおよび１．２ｌのトリエチルアミンの混合物に溶解し、１０℃に冷却し、１．１４ｇ（６ｍｍｏｌ）のヨウ化銅（Ｉ）および８．４２ｇ（１２ｍｍｏｌ）の塩化ビス（トリフェニルホスフィン）パラジウム（ＩＩ）を加えた。バッチを、室温で一晩撹拌し、水およびＭＴＢエーテルを、その後加え、混合物を、さらに５分間撹拌した。反応混合物を、吸引を伴ってセライト(Celite)（登録商標）を通して濾過し、相を分離した。水性相を、ＭＴＢエーテルで２回抽出し、混ぜ合わせた有機相を、３回水で洗浄し、硫酸ナトリウム上で乾燥し、減圧下で蒸発させた。粗製の生成物を、ｎ−ヘプタンを用いてシリカゲルを通して濾過し、１２９ｇの４−ブロモ−２−フルオロ−１−ペント−１−イニルベンゼンが、黄色液体として得られた。ＴＨＦ中のパラジウム／活性炭（１０％）上での水素添加により、１３１ｇ（１００％）の４−ブロモ−２−フルオロ−１−ペンチルベンゼンが、黄色液体として得られた。 Substance examples
Example 1: (4,7-difluoro-8-methyl-3-pentyl-6H-benzo [c] chromen-6-one)
1.1 Preparation of 4-bromo-2-fluoro-1-pentylbenzene

190 g (0.600 mol) 4-bromo-2-fluoro-1-iodobenzene and 65.3 ml 1-pentyne are dissolved in a mixture of 900 ml THF and 1.2 l triethylamine, cooled to 10 ° C., 1.14 g (6 mmol) of copper (I) iodide and 8.42 g (12 mmol) of bis (triphenylphosphine) palladium (II) chloride were added. The batch was stirred overnight at room temperature, water and MTB ether were then added and the mixture was stirred for an additional 5 minutes. The reaction mixture was filtered through Celite® with suction and the phases were separated. The aqueous phase was extracted twice with MTB ether and the combined organic phases were washed three times with water, dried over sodium sulfate and evaporated under reduced pressure. The crude product was filtered through silica gel with n-heptane to give 129 g of 4-bromo-2-fluoro-1-pent-1-ynylbenzene as a yellow liquid. Hydrogenation over palladium / activated carbon (10%) in THF gave 131 g (100%) of 4-bromo-2-fluoro-1-pentylbenzene as a yellow liquid.

１３２ｇ（０．５８３ｍｏｌ）の４−ブロモ−２−フルオロ−１−ペンチルベンゼンを、９００ｍｌのＴＨＦに溶解し、ＬＤＡをＴＨＦに溶解した２モル溶液２９５ｍｌを、−７０℃で滴加した。１時間後、６５．９ｍｌ（０．５９０ｍｏｌ）のホウ酸トリメチルを加え、混合物を、さらに１時間撹拌し、次に１５０ｍｌの５０パーセント酢酸を用いて、−１５℃で酸性化した。バッチを、その後３０℃に加温し、１３９ｍｌ（１．６１ｍｏｌ）の３５パーセント過酸化水素溶液を、滴加した。１時間後、混合物を、水で希釈し、有機相を、分離して除去した。混ぜ合わせた有機相を、硫酸アンモニウム鉄（ＩＩ）溶液で２回および水で１回洗浄し、硫酸ナトリウム上で乾燥し、減圧下で蒸発させた。 1.2 Preparation of 6-bromo-2-fluoro-3-pentylphenol

132 g (0.583 mol) of 4-bromo-2-fluoro-1-pentylbenzene was dissolved in 900 ml of THF, and 295 ml of a 2 molar solution of LDA in THF was added dropwise at -70 ° C. After 1 hour, 65.9 ml (0.590 mol) of trimethylborate was added and the mixture was stirred for an additional hour and then acidified at −15 ° C. with 150 ml of 50 percent acetic acid. The batch was then warmed to 30 ° C. and 139 ml (1.61 mol) of 35 percent hydrogen peroxide solution was added dropwise. After 1 hour, the mixture was diluted with water and the organic phase was separated off. The combined organic phases were washed twice with ammonium iron (II) sulfate solution and once with water, dried over sodium sulfate and evaporated under reduced pressure.

  Filtration of the crude product through silica gel with n-heptane / 1-chlorobutane (3: 1) gave 86.0 g (61% of theory) of 6-bromo-2-fluoro-3-pentyl. Phenol was obtained as colorless crystals.

５０ｍｌ（０．３８５ｍｏｌ）の４−ブロモ−２−フルオロトルエンを、７５０ｍｌのＴＨＦに溶解し、ＬＤＡをＴＨＦに溶解した２Ｍ溶液２３１ｍｌ（０．４６２ｍｏｌ）を、−７０℃で滴加した。７０分後、３７．２ｇ（０．８４６ｍｏｌ）の二酸化炭素を通じ、バッチを、放置して融解させた。濃塩酸を用いた酸性化の後に、溶液を、ＭＴＢエーテルで抽出し、混ぜ合わせた有機相を、水で洗浄し、硫酸ナトリウム上で乾燥し、減圧下で蒸発させた。１−クロロブタンからの粗製の生成物の結晶化により、４４．１ｇ（４９％）の６−ブロモ−２−フルオロ−３−メチル安息香酸が、白色結晶として得られた。 1.3 Preparation of 6-bromo-2-fluoro-3-methylbenzoic acid

50 ml (0.385 mol) of 4-bromo-2-fluorotoluene was dissolved in 750 ml of THF, and 231 ml (0.462 mol) of a 2M solution in which LDA was dissolved in THF was added dropwise at -70 ° C. After 70 minutes, the batch was allowed to melt through 37.2 g (0.846 mol) of carbon dioxide. After acidification with concentrated hydrochloric acid, the solution was extracted with MTB ether and the combined organic phases were washed with water, dried over sodium sulfate and evaporated under reduced pressure. Crystallization of the crude product from 1-chlorobutane gave 44.1 g (49%) of 6-bromo-2-fluoro-3-methylbenzoic acid as white crystals.

４３．２ｇ（０．１６５ｍｏｌ）の６−ブロモ−２−フルオロ−３−ペンチルフェノール、４０．５ｇ（０．１７３ｍｏｌ）の６−ブロモ−２−フルオロ−３−メチル安息香酸および３．５２ｇ（２９ｍｍｏｌ）の４−（ジメチルアミノ）ピリジンを、最初に３００ｍｌのジクロロメタン中に導入し、３５．７ｇ（０．１７２ｍｏｌ）のＮ，Ｎ−ジシクロヘキシルカルボジイミドを８０ｍｌのジクロロメタンに溶解した溶液を加えた。バッチを、室温で一晩撹拌し、その後４．１６ｇ（３３ｍｍｏｌ）のシュウ酸を加えた。１時間後、沈殿した固体を濾別し、濾液を、減圧下で蒸発させた。粗製の生成物を、ｎ−ヘプタン／１−クロロブタン（１：１）を用いてシリカゲルを通して濾過し、７２．７ｇ（理論値の９１％）の６−ブロモ−２−フルオロ−３−メチル安息香酸６−ブロモ−２−フルオロ−３−ペンチルフェニルが、無色油状物として得られた。 1.4 Preparation of 6-bromo-2-fluoro-3-pentylphenyl 6-bromo-2-fluoro-3-methylbenzoate

43.2 g (0.165 mol) 6-bromo-2-fluoro-3-pentylphenol, 40.5 g (0.173 mol) 6-bromo-2-fluoro-3-methylbenzoic acid and 3.52 g (29 mmol) ) 4- (dimethylamino) pyridine was first introduced into 300 ml of dichloromethane and a solution of 35.7 g (0.172 mol) of N, N-dicyclohexylcarbodiimide in 80 ml of dichloromethane was added. The batch was stirred at room temperature overnight, after which 4.16 g (33 mmol) of oxalic acid was added. After 1 hour, the precipitated solid was filtered off and the filtrate was evaporated under reduced pressure. The crude product is filtered through silica gel with n-heptane / 1-chlorobutane (1: 1) and 72.7 g (91% of theory) of 6-bromo-2-fluoro-3-methylbenzoic acid. 6-Bromo-2-fluoro-3-pentylphenyl was obtained as a colorless oil.

５６．２ｇ（１１８ｍｍｏｌ）の６−ブロモ−２−フルオロ−３−メチル安息香酸６−ブロモ−２−フルオロ−３−ペンチルフェニルを、６５０ｍｌのＤＭＦに溶解し、混合物を、４８時間、７５．１ｇ（１．１８ｍｍｏｌ）の銅粉末の存在下で還流させた。その後、混合物を、水で希釈し、酢酸エチルで抽出した。抽出物を混ぜ合わせ、Ｎａ_２ＳＯ_４上で乾燥し、蒸発させた。粗製の生成物を、１−クロロブタンから再結晶し、９．６０ｇのラクトンが、無色固体として得られた。これは、２６％の収率に相当する。
化合物の物理的特性を、以下の表に示す。 1.5 Preparation of 4,7-difluoro-8-methyl-3-pentyl-6H-benzo [c] chromen-6-one

56.2 g (118 mmol) 6-bromo-2-fluoro-3-methylbenzoic acid 6-bromo-2-fluoro-3-pentylphenyl was dissolved in 650 ml DMF and the mixture was dissolved in 75.1 g for 48 hours. Reflux in the presence of (1.18 mmol) of copper powder. The mixture was then diluted with water and extracted with ethyl acetate. The extracts were combined, dried over Na ₂ SO ₄ and evaporated. The crude product was recrystallized from 1-chlorobutane to give 9.60 g of lactone as a colorless solid. This corresponds to a yield of 26%.
The physical properties of the compounds are shown in the table below.

注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 2-120
The following are prepared as in Example 1:

Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

２．００ｇ（６．３３ｍｍｏｌ）の例１からの化合物を、１２ｍｌのＴＨＦに溶解した。２．５６ｍｌ（２３ｍｍｏｌ）の三フッ化ホウ素／ＴＨＦ複合体を、この溶液に氷冷しながら加えた。次に、１２ｍｌのジエチレングリコールジメチルエーテルおよび、分割して、０．５８ｇ（１５ｍｍｏｌ）の水素化ホウ素ナトリウムを、連続して加え、混合物を、室温（約２０℃）で１６時間撹拌した。反応溶液を、氷水を用いて加水分解し、ＭＴＢエーテルで抽出し、抽出物を混ぜ合わせ、Ｎａ_２ＳＯ_４上で乾燥し、蒸発させた。粗製の生成物を、ｎ−ヘプタンから再結晶し、１．６０ｇのベンゾクロメンの無色結晶が得られた。これは、８３％の収率に相当する。 Example 121: (4,7-Difluoro-8-methyl-3-pentyl-6H-benzo [c] chromene)
Preparation of 4,7-difluoro-8-methyl-3-pentyl-6H-benzo [c] chromene

2.00 g (6.33 mmol) of the compound from Example 1 was dissolved in 12 ml of THF. 2.56 ml (23 mmol) of boron trifluoride / THF complex was added to this solution with ice cooling. Then 12 ml diethylene glycol dimethyl ether and in portions 0.58 g (15 mmol) sodium borohydride were added in succession and the mixture was stirred at room temperature (about 20 ° C.) for 16 hours. The reaction solution was hydrolyzed with ice water, extracted with MTB ether, the extracts were combined, dried over Na ₂ SO ₄ and evaporated. The crude product was recrystallized from n-heptane to give 1.60 g of benzochromene colorless crystals. This corresponds to a yield of 83%.

注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 122-240
The following are prepared analogously to Example 121:

Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

４．００ｇ（１１．５ｍｍｏｌ）の例８０からの化合物および５．１４ｇ（１２．７ｍｍｏｌ）のラウェソンの試薬を、６０ｍｌのクロロベンゼンに溶解し、混合物を、４８時間還流させた。その後、バッチを蒸発させ、慣用の精製を施し、２．９０ｇ（８．００ｍｍｏｌ）の対応するチオノラクトンが、オレンジ色の固体として得られた。これは、６９％の収率に相当する。 Example 241 (8-ethoxy-4,6,6,7-tetrafluoro-3-pentyl-6H-benzo [c] chromene)
Preparation of 8-ethoxy-4,6,6,7-tetrafluoro-3-pentyl-6H-benzo [c] chromene

4.00 g (11.5 mmol) of the compound from Example 80 and 5.14 g (12.7 mmol) of Laweson's reagent were dissolved in 60 ml of chlorobenzene and the mixture was refluxed for 48 hours. The batch was then evaporated and subjected to conventional purification to give 2.90 g (8.00 mmol) of the corresponding thionolactone as an orange solid. This corresponds to a yield of 69%.

  Thionolactone was dissolved in 40 ml of dichloromethane. Then 2.1 ml (16.1 mmol) of DAST was added and the mixture was stirred at about 20 ° C. for 16 hours and subjected to conventional purification. The crude product was purified through silica gel using a mixture of n-heptane / ethyl acetate (9: 1) and recrystallized from ethanol to give 0.46 g of difluorobenzochromene. This corresponds to a yield of 15%.

注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 242-360
The following are prepared analogously to Example 241:

Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

２００ｇ（０．６６５ｍｏｌ）の１−ブロモ−３−フルオロ−４−ヨードベンゼンを、８００ｍｌのテトラヒドロフランに溶解し、ｎ−ブチルリチウムをヘキサンに溶解した１５パーセント溶液４４０ｍｌ（０．６９８ｍｍｏｌ）を、−７０℃で滴加した。３０分後、１１７ｇ（０．６９８ｍｏｌ）の４−ペンチルシクロヘキサノンを２００ｍｌのテトラヒドロフランに溶解した溶液を加え、バッチを、６０分間放置して撹拌し、水を用いて加水分解し、濃塩酸を用いて酸性化した。有機相を分離して除去し、水で洗浄し、硫酸ナトリウム上で乾燥し、溶媒を、減圧下で除去した。その後、粗製の生成物を、１．４ｌのトルエンに溶解し、６ｇのトルエンスルホン酸を加えた後に、水分離器上で、反応の水がもはや分離して除去されなくなるまで加熱した。溶液を、水で洗浄し、蒸発させ、残留物を、ｎ−ヘプタンを用いてシリカゲルを介して濾過し、１２４ｇ（５８％）の４−ブロモ−２−フルオロ−１−（４−ペンチルシクロヘクス−１−エニル）ベンゼンが、黄色固体として得られた。 Example 361a: (3-Butoxy-4,6,6,7-tetrafluoro-8- (4-pentylcyclohexyl) -6H-benzo [c] chromene)
361.1 Preparation of 4-bromo-2-fluoro-1- (4-pentylcyclohex-1-enyl) benzene

200 g (0.665 mol) of 1-bromo-3-fluoro-4-iodobenzene was dissolved in 800 ml of tetrahydrofuran and 440 ml (0.698 mmol) of a 15 percent solution of n-butyllithium in hexane was added to -70. Added dropwise at 0 ° C. After 30 minutes, a solution of 117 g (0.698 mol) of 4-pentylcyclohexanone in 200 ml of tetrahydrofuran is added and the batch is left to stir for 60 minutes, hydrolyzed with water and concentrated hydrochloric acid. Acidified. The organic phase was separated off, washed with water, dried over sodium sulfate and the solvent removed under reduced pressure. The crude product was then dissolved in 1.4 l of toluene and 6 g of toluenesulfonic acid was added and heated on a water separator until the water of reaction was no longer separated and removed. The solution was washed with water and evaporated, the residue was filtered through silica gel with n-heptane and 124 g (58%) of 4-bromo-2-fluoro-1- (4-pentylcyclohex -1-enyl) benzene was obtained as a yellow solid.

１２４ｇ（０．３８２ｍｏｌ）の４−ブロモ−２−フルオロ−１−（４−ペンチルシクロヘクス−１−エニル）ベンゼンを、５バールおよび５０℃において、白金／活性化炭素触媒上のテトラヒドロフラン中で完全に水素添加した。濾過および減圧下での溶媒の除去により、１１４ｇ（８０％）のシスおよびトランス−４−ブロモ−２−フルオロ−１−（４−ペンチルシクロヘキシル）ベンゼンの混合物が、黄色油状物として得られた。異性化のために、これを、２００ｍｌのジクロロメタンに溶解し、１２．５ｇ（９５．７ｍｍｏｌ）の塩化アルミニウムを２２０ｍｌのジクロロメタンに懸濁させた懸濁液に滴加した。３０分後、３００ｍｌの水を加え、有機相を分離して除去し、水で洗浄し、硫酸ナトリウム上で乾燥した。溶媒を、減圧下で除去し、残留物を、ｎ−ペンタンを用いてシリカゲルを介して濾過し、５２．８％のトランス−４−ブロモ−２−フルオロ−１−（４−ペンチルシクロヘキシル）ベンゼンの含量および９．７％のシス−４−ブロモ−２−フルオロ−１−（４−ペンチルシクロヘキシル）ベンゼンの含量を有する８５．２ｇの粗製の生成物が、黄色液体として得られ、これを、次の段階においてさらに精製せずに用いた。 361.2 Preparation of 4-bromo-2-fluoro-1- (4-pentylcyclohexyl) benzene

124 g (0.382 mol) of 4-bromo-2-fluoro-1- (4-pentylcyclohex-1-enyl) benzene was completely dissolved in tetrahydrofuran over a platinum / activated carbon catalyst at 5 bar and 50 ° C. Was hydrogenated. Filtration and removal of the solvent under reduced pressure gave a mixture of 114 g (80%) of cis and trans-4-bromo-2-fluoro-1- (4-pentylcyclohexyl) benzene as a yellow oil. For isomerization, it was dissolved in 200 ml of dichloromethane and added dropwise to a suspension of 12.5 g (95.7 mmol) of aluminum chloride in 220 ml of dichloromethane. After 30 minutes, 300 ml of water was added and the organic phase was separated and removed, washed with water and dried over sodium sulfate. The solvent is removed under reduced pressure and the residue is filtered through silica gel with n-pentane to give 52.8% trans-4-bromo-2-fluoro-1- (4-pentylcyclohexyl) benzene. And 85.2 g of crude product having a content of cis-4-bromo-2-fluoro-1- (4-pentylcyclohexyl) benzene of 9.7% are obtained as a yellow liquid, Used in the next step without further purification.

８５．２ｇ（０．１６３ｍｏｌ）の前の段階からの粗製の生成物を、最初に、４００ｍｌのテトラヒドロフラン中に、−７０℃で導入し、ヘキサン中の１５パーセントのｎ−ブチルリチウム２１３ｍｌおよび１００ｍｌのテトラヒドロフラン中の４６ｍｌ（０．３２６ｍｍｏｌ）のジイソプロピルアミンから調製した、リチウムジイソプロピルアミドの溶液を、滴加した。１時間後、２２．９ｇ（０．５２１ｍｏｌ）の二酸化炭素を通じた。バッチを、放置して融解させ、濃塩酸を用いて酸性化し、ＭＴＢエーテルで２回抽出した。混ぜ合わせた有機相を、水で洗浄し、硫酸ナトリウム上で乾燥し、溶媒を、減圧下で除去した。ｎ−ヘプタンからの結晶化により、１７ｇ（２８％）のトランス−６−ブロモ−２−フルオロ−３−（４−ペンチルシクロヘキシル）安息香酸が、無色結晶として得られた。 361.3 Preparation of trans-6-bromo-2-fluoro-3- (4-pentylcyclohexyl) benzoic acid

85.2 g (0.163 mol) of the crude product from the previous step was first introduced into 400 ml of tetrahydrofuran at −70 ° C., and 213 ml of 15 percent n-butyllithium in hexane and 100 ml of A solution of lithium diisopropylamide prepared from 46 ml (0.326 mmol) of diisopropylamine in tetrahydrofuran was added dropwise. After 1 hour, 22.9 g (0.521 mol) of carbon dioxide was passed through. The batch was allowed to melt, acidified with concentrated hydrochloric acid and extracted twice with MTB ether. The combined organic phase was washed with water, dried over sodium sulfate and the solvent was removed under reduced pressure. Crystallization from n-heptane yielded 17 g (28%) of trans-6-bromo-2-fluoro-3- (4-pentylcyclohexyl) benzoic acid as colorless crystals.

１７．１ｇ（４６．０ｍｍｏｌ）のトランス−６−ブロモ−２−フルオロ−３−（４−ペンチルシクロヘキシル）安息香酸を、７０ｍｌのアセトンに溶解し、７．６６ｇ（５５．４ｍｍｏｌ）の炭酸カリウムおよび３．１４ｍｌ（５０．６ｍｍｏｌ）のヨウ化メチルを加え、混合物を、一晩還流させた。バッチを濾過し、溶媒を蒸留して除去し、１８ｇ（１００％）の６−ブロモ−２−フルオロ−３−（４−ペンチルシクロヘキシル）安息香酸メチルが、無色油状物として得られ、これを、さらに精製せずにさらに反応させた。 361.4 Preparation of methyl trans-6-bromo-2-fluoro-3- (4-pentylcyclohexyl) benzoate

17.1 g (46.0 mmol) of trans-6-bromo-2-fluoro-3- (4-pentylcyclohexyl) benzoic acid is dissolved in 70 ml of acetone, and 7.66 g (55.4 mmol) of potassium carbonate and 3.14 ml (50.6 mmol) methyl iodide was added and the mixture was refluxed overnight. The batch was filtered and the solvent was removed by distillation to give 18 g (100%) of methyl 6-bromo-2-fluoro-3- (4-pentylcyclohexyl) benzoate as a colorless oil, Further reaction was carried out without further purification.

例８４１．１および８４１．４と同様にして、４−ブロモ−２−フルオロフェノールにより、６−ブロモ−３−ブトキシ−２−フルオロフェノールが、茶色油状物として得られた（８０％、２段階）。 361.5 Preparation of 1-bromo-4-butoxy-3-fluoro-2- (2-methoxyethoxymethoxy) benzene

Analogously to Examples 841.1 and 841.4, 4-bromo-2-fluorophenol gave 6-bromo-3-butoxy-2-fluorophenol as a brown oil (80%, 2 steps). ).

  60.4 ml (0.355 mol) of ethyldiisopropylamine was added to 77.4 g (0.294 mol) of 6-bromo-3-butoxy-2-fluorophenol dissolved in 500 ml of dichloromethane while cooling with ice. .3 ml (0.355 mol) of 2-methoxyethoxymethyl chloride was added dropwise and the mixture was left to stir overnight at room temperature. The batch is hydrolyzed with water, extracted with dichloromethane, evaporated and the crude product is filtered through silica gel with n-heptane / MTB ether (3: 1) to give 103 g (99% Of 1-bromo-4-butoxy-3-fluoro-2- (2-methoxyethoxymethoxy) benzene in the form of a yellow oil.

１６．４ｇ（０．０４６ｍｏｌ）の１−ブロモ−４−ブトキシ−３−フルオロ−２−（２−メトキシエトキシメトキシ）ベンゼンを、２０ｍｌのテトラヒドロフランに溶解し、ｎ−ブチルリチウムをヘキサンに溶解した１５パーセント溶液３１．６ｍｌ（０．０５２ｍｏｌ）を、−７０℃で加えた。５．９４ｇ（０．０２７ｍｏｌ）の臭化亜鉛を３０ｍｌのテトラヒドロフランに溶解した溶液を加えた後、バッチを放置して融解させ、得られた溶液を、沸点において、６０ｍｌのテトラヒドロフラン中の１８ｇ（０．０４６ｍｏｌ）の６−ブロモ−２−フルオロ−３−（４−ペンチルシクロヘキシル）安息香酸メチルおよび７３０ｍｇ（１．００ｍｍｏｌ）のＰｄ（ｄｐｐｆ）_２Ｃｌ_２の混合物に加えた。バッチを、４時間還流させ、室温で一晩撹拌し、希塩酸を用いて酸性化し、ＭＴＢエーテルで抽出した。 361.6 Preparation of 3-butoxy-4,7-difluoro-8- (4-pentylcyclohexyl) -benzo [c] chromen-6-one

16.4 g (0.046 mol) of 1-bromo-4-butoxy-3-fluoro-2- (2-methoxyethoxymethoxy) benzene was dissolved in 20 ml of tetrahydrofuran, and n-butyllithium was dissolved in hexane. 31.6 ml (0.052 mol) of a percent solution was added at -70 ° C. After adding a solution of 5.94 g (0.027 mol) of zinc bromide in 30 ml of tetrahydrofuran, the batch was allowed to melt and the resulting solution was obtained at the boiling point with 18 g (0 0.046 mol) of methyl 6-bromo-2-fluoro-3- (4-pentylcyclohexyl) benzoate and 730 mg (1.00 mmol) of Pd (dppf) ₂ Cl ₂ . The batch was refluxed for 4 hours, stirred at room temperature overnight, acidified with dilute hydrochloric acid and extracted with MTB ether.

  The combined organic phases were washed with water, dried over sodium sulphate and evaporated. The crude product was chromatographed on silica gel with n-pentane / MTB ether (3: 1) to give 14.6 g (55%) of 4′-butoxy-3,3′-difluoro-2 ′. Methyl-(2-methoxyethoxymethoxy) -4- (4-pentylcyclohexyl) biphenyl-2-carboxylate was obtained as a yellow oil. This was dissolved in 56 ml of tetrahydrofuran, 11 ml of concentrated hydrochloric acid was added and the mixture was stirred at room temperature overnight. The precipitated product is filtered off with suction, washed with ethyl acetate, dried and 7.6 g (68%) of 3-butoxy-4,7-difluoro-8- (4-pentylcyclohexyl) -benzo [C] chromen-6-one was obtained as colorless crystals.

１１．７ｇ（２５．６ｍｍｏｌ）の３−ブトキシ−４，７−ジフルオロ−８−（４−ペンチルシクロヘキシル）−ベンゾ［ｃ］クロメン−６−オンおよび１１．４ｇ（２８．２ｍｍｏｌ）のラウェソンの試薬を、１３０ｍｌのクロロベンゼン中で１６時間還流させた。その後、溶液を、シリカゲルを通して濾過し、蒸発させ、粗製の生成物を、ＭＴＢエーテルからの結晶により精製し、７．９ｇ（６５％）の３−ブトキシ−４，７−ジフルオロ−８−（４−ペンチルシクロヘキシル）ベンゾ［ｃ］クロメン−６−チオンが、黄色結晶として得られた。 361.7 Preparation of 3-Butoxy-4,7-difluoro-8- (4-pentylcyclohexyl) -benzo [c] chromene-6-thione

11.7 g (25.6 mmol) of 3-butoxy-4,7-difluoro-8- (4-pentylcyclohexyl) -benzo [c] chromen-6-one and 11.4 g (28.2 mmol) of Laweson's reagent Was refluxed in 130 ml of chlorobenzene for 16 hours. The solution was then filtered through silica gel, evaporated and the crude product was purified by crystals from MTB ether to yield 7.9 g (65%) of 3-butoxy-4,7-difluoro-8- (4 -Pentylcyclohexyl) benzo [c] chromene-6-thione was obtained as yellow crystals.

２．００ｇ（４．１８ｍｍｏｌ）の３−ブトキシ−４，７−ジフルオロ−８−（４−ペンチルシクロヘキシル）ベンゾ［ｃ］クロメン−６−チオンを、２０ｍｌのジクロロメタンに溶解し、−７０℃に冷却し、ピリジンに溶解したフッ化水素の６５％溶液０．５５ｍｌ（２０ｍｍｏｌ）を加え、２．５６ｇ（８．３６ｍｍｏｌ）の１，３−ジブロモ−５，５−ジメチルヒダントインを１２ｍｌのジクロロメタンに懸濁させた懸濁液を、分割して加えた。２時間後、バッチを、放置して融解させ、飽和炭酸水素ナトリウム溶液を用いて中和し、ジクロロメタンで抽出した。有機相を、水で洗浄し、硫酸ナトリウム上で乾燥し、蒸発させ、粗製の生成物を、ヘプタン／トルエン（１：２）を用いてシリカゲル上でクロマトグラフィー分離した。ｎ−ヘプタンからの結晶化により、１．０ｇ（５２％）の３−ブトキシ−４，６，６，７−テトラフルオロ−８−（４−ペンチルシクロヘキシル）−６Ｈ−ベンゾ［ｃ］クロメンが、融点が９９℃である無色結晶として得られた。 361.8 Preparation of 3-butoxy-4,6,6,7-tetrafluoro-8- (4-pentylcyclohexyl) -6H-benzo [c] chromene

2.00 g (4.18 mmol) of 3-butoxy-4,7-difluoro-8- (4-pentylcyclohexyl) benzo [c] chromene-6-thione is dissolved in 20 ml of dichloromethane and cooled to −70 ° C. Then, 0.55 ml (20 mmol) of a 65% solution of hydrogen fluoride dissolved in pyridine was added, and 2.56 g (8.36 mmol) of 1,3-dibromo-5,5-dimethylhydantoin was suspended in 12 ml of dichloromethane. The resulting suspension was added in portions. After 2 hours, the batch was allowed to melt, neutralized with saturated sodium bicarbonate solution and extracted with dichloromethane. The organic phase was washed with water, dried over sodium sulphate, evaporated and the crude product was chromatographed on silica gel with heptane / toluene (1: 2). Crystallization from n-heptane yields 1.0 g (52%) of 3-butoxy-4,6,6,7-tetrafluoro-8- (4-pentylcyclohexyl) -6H-benzo [c] chromene. Obtained as colorless crystals having a melting point of 99 ° C.

  The compound exhibits the following phase behavior: C 99 ° C. N 130.5 ° C. I, 148 ° C. extrapolated clearing point and 20 ° C. 0.153 extrapolated birefringence and −16.7. Has extrapolated dielectric anisotropy.

式中、

は、

であり、
Ｚ^１は、単結合である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 361b and 362-390
The following are prepared analogously to Example 241 and Example 361a:

Where

Is

And
Z ¹ is a single bond.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

式中、

は、

であり、
Ｚ^１は、−ＣＦ_２−Ｏ−である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 391-420
The following are prepared analogously to Example 241 and Example 361a:

Where

Is

And
Z ¹ is —CF ₂ —O—.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

式中、

は、

であり、
Ｚ^１は、−ＣＨ_２−Ｏ−である。
注：^＊値は、ＺＬＩ−４７９２に溶解した１０％溶液から外挿した。 Examples 421-450
The following are prepared analogously to Example 241 and Example 361a:

Where

Is

And
Z ¹ is —CH ₂ —O—.
Note: ^* Values extrapolated from 10% solution dissolved in ZLI-4792.

式中、

は、

であり、
Ｚ^１は、−ＣＦ＝ＣＦ−である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 451-480
The following are prepared analogously to Example 241 and Example 361a:

Where

Is

And
Z ¹ is —CF═CF—.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

式中、

は、

であり、
Ｚ^１は、単結合である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 481-510
The following are prepared analogously to Example 241 and Example 361a:

Where

Is

And
Z ¹ is a single bond.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

式中、

は、

であり、
Ｚ^１は、−ＣＦ_２−Ｏ−である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 511-540
The following are prepared analogously to Example 241 and Example 361a:

Where

Is

And
Z ¹ is —CF ₂ —O—.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

式中、

は、

であり、
Ｚ^１は、−ＣＨ_２−Ｏ−である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 541-570
The following are prepared analogously to Example 241 and Example 361a:

Where

Is

And
Z ¹ is —CH ₂ —O—.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

式中、

は、

であり、
Ｚ^１は、−ＣＦ＝ＣＦ−である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 571-600
The following are prepared analogously to Example 241 and Example 361a:

Where

Is

And
Z ¹ is —CF═CF—.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

式中、

は、

であり、
Ｚ^１は、単結合である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 601-630
The following are prepared analogously to Example 241 and Example 361a:

Where

Is

And
Z ¹ is a single bond.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

式中、

は、

であり、
Ｚ^１は、−ＣＦ_２−Ｏ−である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 631-660
The following are prepared analogously to Example 241 and Example 361a:

Where

Is

And
Z ¹ is —CF ₂ —O—.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

式中、

は、

であり、
Ｚ^１は、−ＣＨ_２−Ｏ−である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 661-690
The following are prepared analogously to Example 241 and Example 361a:

Where

Is

And
Z ¹ is —CH ₂ —O—.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

式中、

は、

であり、
Ｚ^１は、−ＣＦ＝ＣＦ−である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 691-720
The following are prepared analogously to Example 241 and Example 361a:

Where

Is

And
Z ¹ is —CF═CF—.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

式中、

は、

であり、
Ｚ^１は、単結合である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 721-750
The following are prepared analogously to Example 241 and Example 361a:

Where

Is

And
Z ¹ is a single bond.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

式中、

は、

であり、
Ｚ^１は、−ＣＦ_２−Ｏ−である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 751-780
The following are prepared analogously to Example 241 and Example 361a:

Where

Is

And
Z ¹ is —CF ₂ —O—.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

式中、

は、

であり、
Ｚ^１は、−ＣＨ_２−Ｏ−である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 781-810
The following are prepared analogously to Example 241 and Example 361a:

Where

Is

And
Z ¹ is —CH ₂ —O—.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

式中、

は、

であり、
Ｚ^１は、−ＣＦ＝ＣＦ−である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 811 to 840
The following are prepared analogously to Example 241 and Example 361a:

Where

Is

And
Z ¹ is —CF═CF—.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

１００ｇ（０．５２４ｍｏｌ）の４−ブロモ−２−フルオロフェノールおよび６６．７ｇ（０．６１２ｍｏｌ）の臭化エチルを、２ｌのエチルメチルケトンに溶解し、１８５ｇ（１．３４ｍｏｌ）の炭酸カリウムの存在下で、２４時間還流させた。その後、溶液を濾過し、濾液を蒸発させ、粗製の生成物を、ｎ−ヘキサンを用いてシリカゲルを通して濾過し、１１４ｇ（理論値の９９％）の４−ブロモ−１−エトキシ−２−フルオロベンゼンが、無色液体として得られた。 Example 841: (8-ethoxy-4,7-difluoro-3-benzyloxybenzo [c] chromen-6-one)
841.1 Preparation of 4-Bromo-1-ethoxy-2-fluorobenzene

100 g (0.524 mol) of 4-bromo-2-fluorophenol and 66.7 g (0.612 mol) of ethyl bromide are dissolved in 2 l of ethyl methyl ketone and 185 g (1.34 mol) of potassium carbonate are present. Under reflux for 24 hours. The solution is then filtered, the filtrate is evaporated, the crude product is filtered through silica gel with n-hexane and 114 g (99% of theory) of 4-bromo-1-ethoxy-2-fluorobenzene. Was obtained as a colorless liquid.

上記した（例１．３の下で）合成と同様にして、２３６ｇの４−ブロモ−１−エトキシ−２−フルオロベンゼンにより、１９０ｇ（理論値の６４％）の６−ブロモ−３−エトキシ−２−フルオロ安息香酸が、無色結晶として得られた。 841.2 Preparation of 6-Bromo-3-ethoxy-2-fluorobenzoic acid

Analogously to the synthesis described above (under Example 1.3), 236 g of 4-bromo-1-ethoxy-2-fluorobenzene give 190 g (64% of theory) of 6-bromo-3-ethoxy- 2-Fluorobenzoic acid was obtained as colorless crystals.

上記した（例２．１または８７２．１の下で）合成と同様にして、２５０ｇ（１．３１ｍｏｌ）の４−ブロモ−２−フルオロフェノールおよび１７９ｍｌ（１．５１ｍｏｌ）の臭化ベンジルにより、３６６ｇ（９７％）の１−ベンジルオキシ−４−ブロモ−２−フルオロベンゼンが、無色結晶として得られた。 841.3 Preparation of 1-Benzyloxy-4-bromo-2-fluorobenzene

Analogously to the synthesis described above (under Example 2.1 or 872.1), 366 g with 250 g (1.31 mol) 4-bromo-2-fluorophenol and 179 ml (1.51 mol) benzyl bromide (97%) of 1-benzyloxy-4-bromo-2-fluorobenzene was obtained as colorless crystals.

上記した（例１．２の下で）合成と同様にして、３６６ｇ（１．２７ｍｏｌ）の１−ベンジルオキシ−４−ブロモ−２−フルオロベンゼンにより、２７０ｇ（理論値の７２％）の３−ベンジルオキシ−６−ブロモ−２−フルオロフェノールが、無色結晶として得られる。 841.4 Preparation of 3-Benzyloxy-6-bromo-2-fluorophenol

Analogously to the synthesis described above (under Example 1.2), 366 g (1.27 mol) of 1-benzyloxy-4-bromo-2-fluorobenzene give 270 g (72% of theory) of 3- Benzyloxy-6-bromo-2-fluorophenol is obtained as colorless crystals.

上記した（例１．４の下で）合成と同様にして、２５３ｇ（０．８５１ｍｏｌ）の３−ベンジルオキシ−６−ブロモ−２−フルオロフェノールおよび２４６ｇ（０．９３６ｍｏｌ）の６−ブロモ−３−エトキシ−２−フルオロ安息香酸により、４０５ｇ（理論値の８７％）の６−ブロモ−３−エトキシ−２−フルオロ安息香酸３−ベンジルオキシ−６−ブロモ−２−フルオロフェニルが、無色結晶として得られる。 841.5 Preparation of 3-Benzyloxy-6-bromo-2-fluorophenyl 6-bromo-3-ethoxy-2-fluorobenzoate

Analogously to the synthesis described above (under Example 1.4), 253 g (0.851 mol) of 3-benzyloxy-6-bromo-2-fluorophenol and 246 g (0.936 mol) of 6-bromo-3 With ethoxy-2-fluorobenzoic acid, 405 g (87% of theory) of 6-bromo-3-ethoxy-2-fluorobenzoic acid 3-benzyloxy-6-bromo-2-fluorophenyl as colorless crystals can get.

１０３ｇ（０．１８８ｍｏｌ）の６−ブロモ−３−エトキシ−２−フルオロ安息香酸３−ベンジルオキシ−６−ブロモ−２−フルオロフェニルを、１ｌのＤＭＦに溶解し、１１９ｇ（１．８８ｍｏｌ）の銅粉末の存在下で、７２時間還流させた。その後、バッチを、水で希釈し、酢酸エチルで抽出し、混ぜ合わせた抽出物を、硫酸ナトリウム上で乾燥し、蒸発させた。ＴＨＦからの粗製の生成物の結晶により、１５ｇ（理論値の２１％）の８−エトキシ−４，７−ジフルオロ−３−ベンジルオキシベンゾ［ｃ］クロメン−６−オンが、淡い黄色の結晶として得られた。 841.6 Preparation of 8-Ethoxy-4,7-difluoro-3-benzyloxybenzo [c] chromen-6-one

103 g (0.188 mol) 6-bromo-3-ethoxy-2-fluorobenzoic acid 3-benzyloxy-6-bromo-2-fluorophenyl was dissolved in 1 l DMF and 119 g (1.88 mol) copper Refluxed in the presence of powder for 72 hours. The batch was then diluted with water and extracted with ethyl acetate, and the combined extracts were dried over sodium sulfate and evaporated. The crude product crystals from THF gave 15 g (21% of theory) of 8-ethoxy-4,7-difluoro-3-benzyloxybenzo [c] chromen-6-one as pale yellow crystals. Obtained.

式中、

は、

であり、
Ｚ^２は、−Ｏ−ＣＨ_２−である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 842-881
The following are prepared analogously to Example 841:

Where

Is

And
Z ² is —O—CH ₂ —.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

２．００ｇ（５．２４ｍｍｏｌ）の３−ベンジルオキシ−８−エトキシ−４，７−ジフルオロ−６Ｈ−ベンゾ［ｃ］クロメン−６−オン、例８４１の化合物を、１２ｍｌのＴＨＦに溶解し、２．３７ｍｌ（２３．０ｍｍｏｌ）の三フッ化ホウ素／ＴＨＦ複合体を、氷冷しながら加えた。その後、２４ｍｌのエチレングリコールジメチルエーテルおよび次に分割して５３０ｍｇの水素化ホウ素ナトリウムを加えた。その後、混合物を、室温で１８時間撹拌し、次に氷上に移送した。混合物に、慣用の精製を施し、１．５ｇ（理論値の７８％）の３−ベンジルオキシ−８−エトキシ−４，７−ジフルオロ−６Ｈ−ベンゾ［ｃ］クロメンが、無色結晶として得られた。これらをＴＨＦに溶解し、０．６ｇのＰｄ／Ｃ（５％）の存在下で１バールの圧力において水素添加し、濾過し、蒸発させ、１．２ｇ（理論値の９９％）の８−エトキシ−４，７−ジフルオロ−３−ヒドロキシ−６Ｈ−ベンゾ［ｃ］クロメンが、無色結晶として得られた。 Example 872: (8-Ethoxy-4,7-difluoro-3- (trans-4-vinylcyclohexylmethoxy) -6H-benzo [c] chromene)
872.1 Preparation of 8-Ethoxy-4,7-difluoro-3-hydroxy-6H-benzo [c] chromene

2.00 g (5.24 mmol) of 3-benzyloxy-8-ethoxy-4,7-difluoro-6H-benzo [c] chromen-6-one, the compound of Example 841, was dissolved in 12 ml of THF and 2 37 ml (23.0 mmol) of boron trifluoride / THF complex was added with ice cooling. Then 24 ml ethylene glycol dimethyl ether and then 530 mg sodium borohydride in portions were added. The mixture was then stirred at room temperature for 18 hours and then transferred onto ice. The mixture was subjected to conventional purification, yielding 1.5 g (78% of theory) of 3-benzyloxy-8-ethoxy-4,7-difluoro-6H-benzo [c] chromene as colorless crystals. . They are dissolved in THF, hydrogenated at a pressure of 1 bar in the presence of 0.6 g of Pd / C (5%), filtered and evaporated, 1.2 g (99% of theory) of 8- Ethoxy-4,7-difluoro-3-hydroxy-6H-benzo [c] chromene was obtained as colorless crystals.

１．２ｇ（４．３２ｍｍｏｌ）の８−エトキシ−４，７−ジフルオロ−３−ヒドロキシ−６Ｈ−ベンゾ［ｃ］クロメン、２．１６ｇ（８．６４ｍｍｏｌ）のヨウ化（トランス−４−ビニルシクロヘキシル）メチルおよび６５０ｍｇ（５ｍｍｏｌ）の炭酸カリウムを、１５ｍｌのアセトン中で、１６時間還流させた。次に、混合物を、ＭＴＢエーテル中に移送し、慣用の精製を施し、４６０ｍｇ（理論値の２７％）の８−エトキシ−４，７−ジフルオロ−３−（トランス−４−ビニルシクロヘキシルメトキシ）−６Ｈ−ベンゾ［ｃ］クロメンが、無色結晶として得られた。 872.2 Preparation of 8-ethoxy-4,7-difluoro-3- (trans-4-vinylcyclohexylmethoxy) -6H-benzo [c] chromene

1.2 g (4.32 mmol) 8-ethoxy-4,7-difluoro-3-hydroxy-6H-benzo [c] chromene, 2.16 g (8.64 mmol) iodinated (trans-4-vinylcyclohexyl) Methyl and 650 mg (5 mmol) of potassium carbonate were refluxed in 15 ml of acetone for 16 hours. The mixture is then transferred into MTB ether, subjected to conventional purification and 460 mg (27% of theory) of 8-ethoxy-4,7-difluoro-3- (trans-4-vinylcyclohexylmethoxy)- 6H-benzo [c] chromene was obtained as colorless crystals.

式中、

は、

であり、
Ｚ^２は、−Ｏ−ＣＨ_２−である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 873-902
The following are prepared analogously to Example 872:

Where

Is

And
Z ² is —O—CH ₂ —.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

式中、

は、

であり、
Ｚ^１は、単結合である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 903-934
The following are prepared analogously to Example 241 and Example 361a:

Where

Is

And
Z ¹ is a single bond.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

式中、

は、

であり、
Ｚ^１は、−ＣＨ_２−Ｏ−である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 935-966
The following are prepared analogously to Example 241 and Example 361a:

Where

Is

And
Z ¹ is —CH ₂ —O—.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

式中、

は、

であり、
Ｚ^１は、−ＣＦ_２−Ｏ−である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 967-998
The following are prepared analogously to Example 241 and Example 361a:

Where

Is

And
Z ¹ is —CF ₂ —O—.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

式中、

は、

であり、
Ｚ^１は、単結合である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 999-1030
The following are prepared analogously to Example 241 and Example 361a:

Where

Is

And
Z ¹ is a single bond.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

式中、

は、

であり、
Ｚ^１は、−ＣＨ_２−Ｏ−である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 1031-1062
The following are prepared analogously to Example 241 and Example 361a:

Where

Is

And
Z ¹ is —CH ₂ —O—.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

式中、

は、

であり、
Ｚ^１は、−ＣＦ_２−Ｏ−である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 1063-1093
The following are prepared analogously to Example 241 and Example 361a:

Where

Is

And
Z ¹ is —CF ₂ —O—.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

式中、

は、

であり、
Ｚ^１は、単結合である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 1094 to 1125
The following are prepared analogously to Example 241 and Example 361a:

Where

Is

And
Z ¹ is a single bond.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

式中、

は、

であり、
Ｚ^１は、−ＣＨ_２−Ｏ−である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 1126 to 1157
The following are prepared analogously to Example 241 and Example 361a:

Where

Is

And
Z ¹ is —CH ₂ —O—.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

式中、

は、

であり、
Ｚ^１は、−ＣＦ_２−Ｏ−である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 1158 to 1190
The following are prepared analogously to Example 241 and Example 361a:

Where

Is

And
Z ¹ is —CF ₂ —O—.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

式中、

は、

であり、
Ｚ^１は、単結合である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 1191-1222
The following are prepared analogously to Example 241 and Example 361a:

Where

Is

And
Z ¹ is a single bond.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

式中、

は、

であり、
Ｚ^１は、−ＣＨ_２−Ｏ−である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 1223-1254
The following are prepared analogously to Example 241 and Example 361a:

Where

Is

And
Z ¹ is —CH ₂ —O—.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

式中、

は、

であり、
Ｚ^１は、−ＣＦ_２−Ｏ−である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 1255-1286
The following are prepared analogously to Example 241 and Example 361a:

Where

Is

And
Z ¹ is —CF ₂ —O—.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

式中、

は、

であり、
Ｚ^１は、単結合である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 1287-1318
The following are prepared analogously to Example 241 and Example 361a:

Where

Is

And
Z ¹ is a single bond.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

式中、

は、

であり、
Ｚ^１は、−ＣＨ_２−Ｏ−である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 1319 to 1350
The following are prepared analogously to Example 241 and Example 361a:

Where

Is

And
Z ¹ is —CH ₂ —O—.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

式中、

は、

であり、
Ｚ^１は、−ＣＦ_２−Ｏ−である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 1351-1382
The following are prepared analogously to Example 241 and Example 361a:

Where

Is

And
Z ¹ is —CF ₂ —O—.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

式中、

は、

であり、
Ｚ^１は、単結合である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 1383 to 1385
The following are prepared analogously to Example 241 and Example 361a:

Where

Is

And
Z ¹ is a single bond.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

式中、

は、

であり、
Ｚ^１は、−ＣＨ_２−Ｏ−である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 1415-1446
The following are prepared analogously to Example 241 and Example 361a:

Where

Is

And
Z ¹ is —CH ₂ —O—.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

式中、

は、

であり、
Ｚ^１は、−ＣＦ_２−Ｏ−である。
注：^＊値は、ＺＬＩ−４７９２またはＺＬＩ−２８５７に溶解した１０％溶液から外挿した（Δε）。 Examples 1447 to 1478
The following are prepared analogously to Example 241 and Example 361a:

Where

Is

And
Z ¹ is —CF ₂ —O—.
Note: ^* Values were extrapolated from 10% solutions dissolved in ZLI-4792 or ZLI-2857 (Δε).

Mixture Examples Liquid crystal mixtures are prepared and their applicable properties are examined.

液晶媒体は、極めて良好な適用的な特性を有する。 Example M-1
Liquid crystal mixtures having the compositions shown in the following table were prepared and tested. This also has the properties shown in the table.

Liquid crystal media have very good applicable properties.

液晶媒体は、極めて良好な適用的な特性を有する。 Example M-2
Liquid crystal mixtures having the compositions shown in the following table were prepared and tested. This also has the properties shown in the table.

Liquid crystal media have very good applicable properties.

液晶媒体は、優れた適用的な特性を有する。 Example M-3
Prepare and inspect the mixture shown in the table below.

Liquid crystal media have excellent applicable properties.

液晶媒体は、例えば以下の比較例（ＣＭ−１）と比較して明らかなように、優れた適用的な特性を有する。 Example M-4
Prepare and inspect the mixture shown in the table below.

The liquid crystal medium has excellent applicable characteristics, as is apparent from, for example, the following comparative example (CM-1).

液晶媒体は、透明点、複屈折および誘電異方性について、例Ｍ−４の媒体に類似した値を有する。しかし、これは、顕著に一層高い回転粘度および同時に一層高いしきい値電圧を有し、従って明らかに劣った適用的な特性を有する。
Comparative Example CM-1
The mixtures shown in the table below, which do not contain the compounds of the invention, are prepared and tested.

The liquid crystal medium has similar values for the clearing point, birefringence and dielectric anisotropy as the medium of Example M- 4. However, it has a significantly higher rotational viscosity and at the same time a higher threshold voltage, and thus has clearly poor application properties.

液晶媒体は、例えば以下の比較例（ＣＭ−２）と比較して明らかなように、優れた適用的な特性を有する。 Example M-5
Prepare and inspect the mixture shown in the table below.

The liquid crystal medium has excellent applicable characteristics, as is apparent from, for example, the following comparative example (CM-2).

液晶媒体は、透明点、複屈折および誘電異方性について、例Ｍ−５の媒体に類似した値を有する。しかし、これは、顕著に一層高い回転粘度および同時に一層高いしきい値電圧を有し、従って比較的好適でない適用的な特性を有する。
Comparative Example CM-2
The mixtures shown in the table below, which do not contain the compounds of the invention, are prepared and tested.

The liquid crystal medium has similar values to the medium of Example M- 5 for clearing point, birefringence and dielectric anisotropy. However, it has a significantly higher rotational viscosity and at the same time a higher threshold voltage and therefore has a relatively unsuitable application characteristic.

Claims (10)

Formula I

Where
Y is —CH ₂ —, —CF ₂ — or —CHF—,
L ¹ and L ² are each independently F, and

Are each independently of each other and, if present more than once, also independently of each other,
(A) a trans-1,4-cyclohexylene group, wherein one or two non-adjacent CH ₂ groups may be substituted by —O— and / or —S—;
(B) 1,4-cyclohexenylene group,
(C) 1,4-phenylene group, or (d) 1,4-bicyclo [2.2.2] octylene, wherein one or two non-adjacent CH groups may be substituted by N 1,3-bicyclo [1.1.1] pentylene, spiro [3.3] heptane-2,4-diyl, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2 , 6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl, a group selected from the group consisting of
R ¹ and R ² are each independently of each other H, halogen, —CN, —SCN, —SF ₅ , —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ or CN or CF ₃ is monosubstituted or at least monosubstituted by halogen, wherein one or more CH ₂ groups are each independently of one another O or S atoms. -O-, -S-, -CH = CH-, -CF = CF-, -CF = CH-, -CH = CF-,

An alkyl group having 1 to 15 carbon atoms, optionally substituted by -CO-, -CO-O-, -O-CO- or -O-CO-O-;
Z ¹ and ^{Z 2} are each, independently of one _{another, -CH 2 -CH 2 -, -} CF 2 -CF 2 -, - CF 2 -CH 2 -, - CH 2 -CF 2 -, - CH = CH —, —CF═CF—, —CF═CH—, —CH═CF—, —C≡C—, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O— , —OCF ₂ —, a single bond or a combination of two of these groups, wherein no two O atoms are bonded to each other;
n and m are each 0, 1 or 2, where
n + m is 0, 1, 2 or 3.
A compound represented by Formula I- 2 or I-3

In which the parameters are as defined in claim 1;
The compound of formula I according to claim 1, wherein the compound is selected from the group consisting of compounds represented by: The compound according to claim 1, wherein Y is —CF ₂ —. The compound according to any one of claims 1 to 3, wherein Z ¹ and Z ² are both a single bond. A liquid crystal medium comprising one or more compounds represented by the formula I defined in any one of claims 1 to 4 . Formula II

Where
R ²¹ and R ²² are each, independently of one another, as defined for R ¹ under Formula I in claim 1;
Z ²¹ and Z ²² are each independently of one another as defined for Z ¹ under Formula I in claim 1;

Are independent of each other,

And
L ¹ and L ² are both C—F, or one of the two is N and the other is C—F;
l is 0 or 1;
The liquid crystal medium according to claim 5 , comprising one or more kinds of dielectrically negative compounds represented by: Formula II-1

In the formula, R ²¹ , R ²² , Z ²¹ , Z ²² ,

And l are as defined in claim 6 ;
The liquid crystal medium according to claim 6 , comprising one or more compounds represented by the formula: Use of a liquid crystal medium according to any one of claims 5 to 7 in an electro-optical display. An electro-optic display comprising the liquid crystal medium according to any one of claims 5 to 7 . 10. Display according to claim 9 , characterized in that it is a VAN LCD.